Santagati Tesi

Ai miei genitori
i
ii
Contents
Introduction xiii
1 Inelastic X-ray Scattering 1
1.1 Kinematics and double dierential cross section . . . . . . . . 2
1.2 Experimental aspects . . . . . . . . . . . . . . . . . . . . . . . 11
1.2.1 The IXS spectrometer . . . . . . . . . . . . . . . . . . 14
1.2.2 Energy band-width . . . . . . . . . . . . . . . . . . . . 16
1.2.3 Quasi-backscattering geometry . . . . . . . . . . . . . . 19
1.2.4 Energy scan . . . . . . . . . . . . . . . . . . . . . . . . 21
1.2.5 Spherical Crystal Analyser . . . . . . . . . . . . . . . . 22
1.3 Double pass spectrometer . . . . . . . . . . . . . . . . . . . . 24
2 The experiment 29
2.1 ID 16 beamline at the ESRF . . . . . . . . . . . . . . . . . . . 29
2.2 Spectrometers . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.2.1 Spectrometer in single pass . . . . . . . . . . . . . . . 32
2.2.2 Spectrometer in double pass . . . . . . . . . . . . . . . 36
2.3 Detector unit . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.4 Experimental methods . . . . . . . . . . . . . . . . . . . . . . 39
2.4.1 Alignment and focusing . . . . . . . . . . . . . . . . . 39
iii
2.4.2 Data collection and Compensation . . . . . . . . . . . 45
3 Ray tracing 53
3.1 X-ray ray tracing . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.2 SHADOW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
3.3 X-ray ray tracing by SHADOW . . . . . . . . . . . . . . . . . 57
3.3.1 Source . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.3.2 Analysers . . . . . . . . . . . . . . . . . . . . . . . . . 59
3.3.3 The optical system . . . . . . . . . . . . . . . . . . . . 62
3.4 Ray tracing results . . . . . . . . . . . . . . . . . . . . . . . . 63
3.4.1 Resolution functions: DP spectrometer vs SP one . . . 64
4 Two spectrometers in comparison 73
4.1 Resolution curves . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.1.1 Instrumental function using the Si(444) set of planes . 74
4.1.2 Instrumental function using the Si(555) set of planes . 79
4.1.3 Intensity loss . . . . . . . . . . . . . . . . . . . . . . . 81
4.2 Data from samples . . . . . . . . . . . . . . . . . . . . . . . . 85
4.3 Liquid water vibrational excitations . . . . . . . . . . . . . . . 86
4.3.1 Theoretical background . . . . . . . . . . . . . . . . . . 86
4.3.2 Experimental results: SP spectrometer vs DP one . . . 91
4.3.3 Comparison to other techniques . . . . . . . . . . . . . 94
4.3.4 Further considerations . . . . . . . . . . . . . . . . . . 101
4.4 Test on NiO powder: d-d excitations . . . . . . . . . . . . . . 104
4.4.1 NiO measurements . . . . . . . . . . . . . . . . . . . . 106
Conclusions 109
Acknowledgements 111
iv
Bibliography 115
v
vi
List of Figures
1.1 Kinematics of scattering process . . . . . . . . . . . . . . . . . 2
1.2 Schematics of an excitation spectrum . . . . . . . . . . . . . . 11
1.3 Schematic representation of a storage ring . . . . . . . . . . . 12
1.4 Schematic representation of an undulator . . . . . . . . . . . . 14
1.5 Schematic representation of a triple axis spectrometer . . . . . 15
1.6 Bragg diraction . . . . . . . . . . . . . . . . . . . . . . . . . 16
1.7 Absorption length and extinction length . . . . . . . . . . . . 18
1.8 Rowland circle geometry . . . . . . . . . . . . . . . . . . . . . 22
1.9 Spherical Si diced analyser. . . . . . . . . . . . . . . . . . . . 24
1.10 Schematic of a spectrometer with four axis elements . . . . . . 26
2.1 Beamline layout scheme . . . . . . . . . . . . . . . . . . . . . 31
2.2 Experimental set up - top view . . . . . . . . . . . . . . . . . 32
2.3 Experimental set up - frontal view . . . . . . . . . . . . . . . . 33
2.4 Photo of the experimental set up . . . . . . . . . . . . . . . . 34
2.5 ID16 beamline . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.6 Single pass spectrometer schematic design . . . . . . . . . . . 35
2.7 Analyser chamber . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.8 Double pass spectrometer scheme . . . . . . . . . . . . . . . . 37
2.9 CMOS pixel read-out chip . . . . . . . . . . . . . . . . . . . . 38
2.10 Alignment procedure . . . . . . . . . . . . . . . . . . . . . . . 41
vii
2.11 Focusing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.12 Channel cut . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.13 dzscan concept. . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.14 Image acquired using the single analyser spectrometer . . . . . 48
2.15 Results of data analysed using the PSD . . . . . . . . . . . . . 51
2.16 Shielding on the spectrometer . . . . . . . . . . . . . . . . . . 52
2.17 Shielding eect on the background . . . . . . . . . . . . . . . 52
3.1 Two-mirrors optical system . . . . . . . . . . . . . . . . . . . 56
3.2 Optical element geometry . . . . . . . . . . . . . . . . . . . . 56
3.3 Typical Gaussian source . . . . . . . . . . . . . . . . . . . . . 59
3.4 Spherical mirror in Shadow . . . . . . . . . . . . . . . . . . . 60
3.5 Spherical diced mirror by Matlab . . . . . . . . . . . . . . . . 61
3.6 Schematic representation of the optical system . . . . . . . . . 63
3.7 Ray tracing resolution functions - 3 reections . . . . . . . . . 65
3.8 Comparison ray tracing: DP vs SP
2
. . . . . . . . . . . . . . . 67
3.9 Ray tracing comparison: SP vs DP . . . . . . . . . . . . . . . 69
3.10 Image size reduction . . . . . . . . . . . . . . . . . . . . . . . 72
4.1 Single analyser spectrometer resolution curve . . . . . . . . . . 76
4.2 Double analyser spectrometer resolution curve . . . . . . . . . 77
4.3 Resolutions comparison, SP and DP . . . . . . . . . . . . . . . 80
4.4 Comparison (Si(555)): SP vs DP . . . . . . . . . . . . . . . . 82
4.5 Resolutions comparison:intensity loss . . . . . . . . . . . . . . 84
4.6 Main vibrations occurring in water . . . . . . . . . . . . . . . 87
4.7 Infra-red spectroscopy of water . . . . . . . . . . . . . . . . . 90
4.8 vibrational excitation: DP vs SP . . . . . . . . . . . . . . . . 92
4.9 Liquid water vibrational excitations by DP spectrometer . . . 93
viii
4.10 Water spectrum measured with Si(555) reection . . . . . . . 95
4.11 Dispersion of the stretching peak position . . . . . . . . . . . 96
4.12 Comparison with data collected by the ID16 team . . . . . . . 98
4.13 Comparison to other techniques . . . . . . . . . . . . . . . . . 100
4.14 Gaussian t of the O H stretching peak . . . . . . . . . . . 101
4.15 Fit on the overtone . . . . . . . . . . . . . . . . . . . . . . . . 103
4.16 NiO d-d excitations . . . . . . . . . . . . . . . . . . . . . . . . 105
4.17 Comparison of NiO: SP vs DP . . . . . . . . . . . . . . . . . . 107
ix
x
List of Tables
3.1 Ray tracing settings . . . . . . . . . . . . . . . . . . . . . . . . 64
3.2 Ray tracing FWHM . . . . . . . . . . . . . . . . . . . . . . . . 66
3.3 Source and pixel size contribution to the FWHM . . . . . . . 68
3.4 Ray tracing intensity loss . . . . . . . . . . . . . . . . . . . . . 70
4.1 Width contribution for the instrumental function (Si(444)) . . 74
4.2 Width contribution to the instrumental function (Si(555)) . . 81
4.3 Main characteristics of the DP and SP spectrometers . . . . . 83
4.4 Contributions to intensity loss . . . . . . . . . . . . . . . . . . 83
4.5 Water normal modes in the vapour state . . . . . . . . . . . . 88
4.6 Stretching peak dispersion . . . . . . . . . . . . . . . . . . . . 95
4.7 Stretching and bending excitations, rough values . . . . . . . . 99
xi
xii
Introduction
Inelastic X-ray Scattering (IXS) is a momentum-resolved technique for study-
ing dynamics and excitations in condensed matter systems. Due to the rapid
development in the instrumentation at the synchrotron radiation facilities
able to produce intense and tunable radiation, the inelastic x-ray scatter-
ing technique has improved reaching a high level of precision in studying
a large range of physical processes, with the possibility of controlling both
energy and momentum transfer. In particular the energy spectrum of high-
resolution non resonant inelastic x-ray scattering is easy to be understood in
terms of the atomic dynamic structure factor S(Q, E) (where q and E are the
momentum and the energy transfer) traditionally measured by inelastic light
and neutron scattering. Nowadays, IXS can be considered as an established
tool to measure the atomic S(Q, E), in a few cases extending and more in
general complementing INS (Inelastic Neutron Scattering) techniques [1].
In order to obtain a good measurement of S(Q, E), well collimated and
monochromatic x-rays with a spectral width smaller than the excitation en-
ergies of interest are needed. The available x-ray sources are very bright and
well collimated, however, they are far from being monochromatic. X-ray op-
tics has to be utilized, capable of monochromatizing the radiation from the
x-ray source and analysing the scattered radiation with the required resolu-
tion [2]. In fact the collected spectrum is proportional to the the convolution
xiii
of the double dierential cross section with the instrumental function. It is
then simple to connect the quality of a spectrometer to its resolution power.
For example some kind of excitations, as water molecular vibrational excita-
tions, were basically not measured until now because of limitations coming
from the resolution power.
Many eorts, in the last two decades, to improve the resolution power
of inelastic x-ray scattering spectrometers have been made [3][4][5][6]. This
thesis presents a further step to improve instrumental function of inelastic x-
ray spectrometers, describing the realization and commissioning of a double
analyser spectrometer for inelastic x-ray scattering.
The idea of implementing a double pass spectrometer to improve the in-
strumental resolution is well known in light scattering optics, where several
examples of spectrometers with a similar design are available [7]. The ap-
plication of this idea to x-ray spectrometers is made dicult by the fact
that x-ray optics is by for less advanced in terms of experimental realization
than visible optics. This causes a high level of intensity loss, degrading the
theoretical performances of these instruments. For this reason there are no
examples of double analyser spectrometers for inelastic x-ray scattering, and
this work presents the rst attempt in this direction.
This thesis work has been carried out during an internship of the candi-
date at the ID16 beamline of the ESRF (European Synchrotron Radiation
Facility), where the measurements presented in this work were performed.
In this work I will clarify the aim of the double analyser spectrometer (i.e.
to improve the contrast of the instrumental resolution function), describe
the double analyser spectrometer, simulate its characteristic by ray tracing
and nally test its experimental realization comparing a single pass (SP)
spectrometer with a double pass (DP) one. In the last part of this work I
xiv
performed measurements of molecular vibrational excitations of water and
compared the results with those obtained by other techniques.
In Chapter 1 a theoretical introduction is presented, starting with dis-
cussion of the kinematics of the inelastic scattering process and its double
dierential cross section. In particular, I report the relation between this
last quantity and the atomic dynamic structure factor S(Q, E), which gives
access to the physical information of interest here. After that, the most im-
portant experimental aspects of this technique are reported, starting with a
description of the single pass spectrometer and of its components and ending
with a brief presentation of the double pass spectrometer and its expected
performances.
In Chapter 2 the experimental apparatus and the procedures I followed
are described in detail. This chapter is made of two parts: in the rst part
the ID16 beamline at the ESRF and all the elements composing the two
utilized spectrometers (SP and DP) are presented; in the second part all the
experimental procedures, such as alignment, focusing and data collection, are
exposed.
Before passing to the experimental stage, it was important to predict
the response of the spectrometers, in order to optimize it. For this reason
ray tracing simulations of the system were performed. After a presentation
of the ray tracing software in Chapter 3, the optical system design is de-
scribed. In the last section of this chapter the results obtained by ray tracing
are presented. The comparison, performed by ray tracing, between the SP
spectrometer and the DP one pointed out an improvement of the resolution
power. Furthermore the ray tracing highlighted a stronger reduction of the
resolution function tails in the second case than in the rst one (i.e. an im-
provement in contrast) but it demonstrated also a loss in intensity for the
xv
double pass conguration.
In the last chapter (Chapter 4) of this work the experimental data, col-
lected during the experimental session, are presented. Chapter 4 is also
structured in two parts: In the rst part the measurements concerning the in-
strumental resolution of the two available congurations of the spectrometer
are reported, evidencing better results for the DP spectrometer; in the second
part, instead, measurements concerning two dierent samples are presented.
The choice of suitable samples to test the DP spectrometer was crucial. In
fact it was necessary to look for excitations compatible with the resolution of
the instrument. Two interesting cases compatible with the obtained values
of the FWHM (Full Width at Half Maximum) are: the molecular vibrational
excitations in liquid water, and the d d excitations in NiO. In particular
in the section concerning the liquid water molecular excitations the energy
position of the O-H stretching band has been obtained with good precision.
After that a comparison with the results obtained by other techniques (light
and neutron scattering) is presented to check the reliability of the double
analyser spectrometer measurements.
xvi
Chapter 1
Inelastic X-ray Scattering
To understand the dynamics of matter and resolve both length (momentum)
and time (energy), spectroscopic techniques are needed. Techniques, which
use visible or infra-red light, such as Raman scattering, Brillouin scattering,
and photon correlation techniques can probe the dynamics of matter over a
very large range on the time scale from femtoseconds to seconds. However,
the resolution on the length scale is determined by the wavelength of the
probe and is limited therefore to hundreds of nanometres at best. Radiation
with shorter wavelengths is needed, for example, to access the atomic-scale
dynamics [2]. X-rays with energies E 5keV can be used to probe the
dynamics on this scale.
Inelastic X-ray scattering is the technique used at beamline ID16 of the
ESRF. IXS allows both the energy and the momentum transfer to be con-
trolled in rather wide regions, which makes it possible the study of quite
distinct physical (and chemical) problems in condensed matter, including
phonon-like excitations as well as valance and core electron excitations. This
technique is an established tool which largely proted from the availability
of 2
nd
and 3
rd
generation synchrotron radiation sources [8] [9].
2 1. Inelastic X-ray Scattering
In this chapter a brief description of the inelastic x-ray scattering tech-
nique is reported, focusing in particular the X-ray Inelastic Non Resonant
Scattering (NR-IXS).
1.1 Kinematics and double dierential cross
section
In a typical IXS experiment a well collimated x-ray beam with an energy
1
, momentum k
1
and polarization
1
hits on a sample and the scattered
photons
1
, with an energy
2
, momentum k
2
and polarization
2
are anal-
ysed as a function of the exchanged energy [10] [3]. In gure 1.1 a generic
scattering process is sketched.
Figure 1.1: Kinematics of the inelastic scattering process
The scattered photons carry information on the spectrum of the excita-
tions of energy
=
1
2
(1.1)
1
the probe is scattered in a solid angle around an angle , where is the angle
between the direction of the incoming particle and the direction of observation. is also
called scattering angle.
1.1. Kinematics and double dierential cross section 3
and momentum
Q = k
1
k
2
(1.2)
which are created (or destroyed) in the target during the interaction [10].
From the last relation it is easy to obtain Q
2
= k
2
1
+ k
2
2
2k
1
k
2
cos(). In
cases where the energy transfer is much smaller than the incident photon
energy
2
, i.e.
1
, Q is only controlled by the scattering angle , and
it is given by the following expression:
Q = 2 k
1
sin(/2) (1.3)
There are not special limitations in energy transfer for a dened Q. Usu-
ally in an IXS experiment the energies of the probe are quite higher than
those of any excited state, thus the condition
1
is usually valid.
For example, in this thesis work H
2
O vibrational molecular excitations (or-
der of hundreds of meV) and d d electronic excitations (1 6 eV) were
probed. These excitations correspond to energies lower than that the used
probe (8 10keV). So the prerequisite of equation 1.3 is well satised, and
the approximation is valid.
In an IXS experiment the double dierential cross-section (DDCS) d
2
/(dd
2
)
is measured as a function of Q and , where the DDCS is dened as follows:
d
2
dd
2
=
I
2
[, d][
2
, d
2
]
I
1
d d
2
(1.4)
where I
1
is the current density of incident photons, and I
2
[, d][
2
, d
2
]
is the current of photons scattered into the solid angle element [, d] and
into the range of energy [
2
, d
2
]. The DDCS can be expressed by the
2
E(k) = ck
probability per unit of time,

P
12
, to have a transition of the photon from
the initial state 1 to the nal state 2, id est:
E
=

2
n
E
P
12
v
(1.5)
where is the density of the incident particles inside the V volume of the
sample, v is then velocity and

2
n
E
is the scattered particles density of states.
In the photons case, v = c/V and
2
n
E
=
V
(2)
3
k
2
f
c
(1.6)
The transition between the initial (1) and nal (2) states of the radiation
includes also all the possible elementary excitations taking place in the sam-
ple, so

P
12
is just the sum of all the possible transitions between the initial
state I and the nal one F:
P
12
=
I,F
P
1,IF,2
(1.7)
To calculate the transition probability it is necessary to use the pertur-
bation theory, and so an expression of the interaction Hamiltonian is needed.
The dierent branches of inelastic scattering (i.e. non resonant IXS, non
resonant IXS in the Compton limit and Resonant IXS), dier according to the
relevant Hamiltonian terms describing the interaction of the electro-magnetic
eld represented by its vector potential A with the non relativistic electron
system[3]. Deriving the interaction Hamiltonian H
int
from the kinetic energy
operator [(p eA/c)
2
/2m], it is possible to see that contains an A
2
and a
p A term.
In the non-relativistic limit, the coupling of the electromagnetic eld to
the scattering electron system is described by the following interaction Hamil-
tonian:
H
int
=
j
e
2
2mc
2
A
2
j
+
j
e
mc
A
j
p
j
(1.8)
where the summation is over the electrons of the scattering system. A
is the vector potential of the electromagnetic eld, p is the momentum op-
erator of the scattering electrons, e the elementary charge, m the mass of
the electron, and c the speed of light. To rst order in perturbation theory,
the rst term of equation 1.8 describes the scattering of the photon from
the electric charge of electrons (Thomson scattering) and the second one de-
scribes the absorption or the emission of a photon by the electrons system
(photo-electric eect). In this formulation of the Hamiltonian the terms of
spin-orbit coupling and the one regarding the spin-magnetic eld of photons
interaction were neglected
3
. Also the interaction between photons and nu-
clei is negligible because the coupling between the electromagnetic eld and
the scattering system is inversely proportional to the mass of the charged
particles. So the interaction with the nuclei is smaller than that with the
electrons one of a factor m
e
/m
N
. Here m
e
is the electron mass and m
N
is
the nuclear one.
The transition probability (equation 1.7) to the rst order of the pertur-
bation theory is obtained by the Fermis golden rule:
P
1,IF,2
=
2
|
1
I
|H
int
|
2
F
|
2
(E
1
+ E
I
E
2
E
F
) (1.9)
while for the second order it is expressed by:
3
The two neglected terms are H
spinmagn
=
e
mc
j
s
j
(A
j
) and H
spinorbit
=
e
2
2m
2
c
4
j
s
j

_

A
j
A
j
_
.
P
1,IF,2
=
2
n,N
I
|H
int
|
n
N

n
N
|H
int
|
2
E
1
+ E
I
E
n
E
N
2
(E
1
+ E
I
E
2
E
F
)
(1.10)
where
1,2
are the e.m. radiation states,
I,F
are the material ones, and
the sum is over all the intermediate states |
n
N
.
The nal treatment of the total scattering amplitude including rst and
second order terms is somewhat complicated by the fact that the magnetic
part of the second-order term contributes to the scattering also o-resonance.
Therefore, the magnetic scattering amplitude contains, also o-resonance, a
spin and an orbital contribution.
It is the Thomson charge scattering amplitude which gives rise to scat-
tering from time-dependent density uctuations of the electron system and
forms the basis of that branch of inelastic X-ray scattering which brings direct
experimental access to the time-dependent two particle density correlation,
the main ingredient of the dynamic structure factor S(Q, ) [3], via
d
2
dd
2
=
_
e
2
mc
2
_
2
(
1

2
)
_
1
_
S(Q, ) (1.11)
S(Q, ) =
1
2
_

dtexp(t)
_
d
3
r
_
d
3
rexp(iQr)n
2
(r, r
, t) (1.12)
where
1
and
2
are the polarization vectors and n
2
(r, r
, t) is the time-
dependent two-particle density correlation function, dened as
n
2
(r, r
, t) (r
, t = 0)(r
+r, t) (1.13)
(r, t)
j
(r r
j
(t)) (1.14)
denotes the ground state expectation value of the density operator
product and the summation is over all scattering particles. So, in the classical
limit, n
2
(r, r
, t) gives the probability of nding an electron at time t at r
+r,
if an electron at time t = 0 was at position r
[3].
These last three equations relate IXS with scattering from time-dependent
electron density uctuations.
The DDCS can also be related to excitations of the system (many body)
from the initial ground state |
I
with energy E
I
to all excited nal states
|
F
with energy E
F
, that are allowed according to energy conservation.
Treating the scattering process to the second-order perturbation theory,
representing the vector potential A in terms of photon creation and annihi-
lation operators, and assuming that both initial and nal photon states can
be represented by plane waves, one obtains for the double dierential cross
section[11]:
E
=
_
e
2
mc
2
_
2
_
k
2
k
1
_
I,F
P (E
I
)
F
|
j
e
iQr
j
|
I
(
1

2
) + B
2
(E
F
E
I
)
(1.15)
where B is:
B =
1
m
F
|
2
j
p
j
e
ik
2
r
j
|
N

N
|
1
j
p
j
e
ik
1
r
j
|
I
(E
I
E
N
)
1
+ i
N
+
+
F
|
1
j
p
j
e
ik
1
r
j
|
N

N
|
2
j
p
j
e
ik
2
r
j
|
I
(E
I
E
N
)
2
+ i
N
(1.16)
The sum in the second term B is over all the intermediate states |
N
with
energy E
N
of the system. P(E
I
) is the statistic weight (i.e. the probability)
of the initial state, and Q is the momentum transfer from the photon to
the system. To keep into account the limited lifetime of the intermediate
electronic states, the imaginary term i
N
in the denominator of equation
1.16 was introduced. In fact making its formulation explicit
N
= /
N
,
where
N
is the lifetime of the considered state. The energy conservation
insuring delta function simply states that the energy transfer to the system,
E
F
E
I
, equals the dierence between incident and scattered photon energy,
=
1
2
.
If interference terms are neglected, the cross section is composed of three
contributions. The rst term, derived from A
2
(equation 1.8) in rst or-
der perturbation, describes the non-resonant IXS. The second and the third
terms (composing the two parts of the B term 1.16) are derived from the
A p in second order perturbation theory. The second term (the rst of
B,equation 1.16) describes an absorption process followed by an emission
process, coupled via an intermediate state |
N
, leading to an increase of
the cross section, whenever the energy of the incident photon is close to an
absorption edge of the element under study (E
N
E
I

1
). The enhance-
ment of the IXS cross section is proportional to the transition probability
between |
I
and |
N
,
2
1
, and 1/
2
N
. The third term (the second of B,
equation 1.16) does not display a resonant behaviour, and it can be shown
[3] that this term is smaller by (4
1
/
N
)
2
than the resonant term, and can
therefore be neglected in practical cases.
As it is clear from its formulation the B term is strictly connected to the
incident and emerging photon energies. In fact if E
N
E
I
=
1
(or E
I

E
N
=
2
), the photon is in resonance with a specic electronic transition
and the B term becomes dominant.
When the resonance condition
1
= E
N
E
I
(1.17)
is not satised, Non Resonant Inelastic X-Ray Scattering occurs.
So, in this case it is possible to demonstrate that the second order contri-
bution is negligible and the DDCS depends only on the Thomson scattering
term[11]:
E
= r
2
0
k
2
k
1
I,F
P(E
I
)
F
|
j
e
iQr
j
|
I
(
1

2
)
2
(E
F
E
I
)
(1.18)
where r
0
= e
2
/mc
2
is the classical electron radius.
Equation 1.18 reveals access to a certain symmetry selectivity of non-
resonant inelastic X-ray scattering spectroscopy, since the matrix element is
subject to symmetry-related selection rules [3]. The most important feature
of non resonant inelastic x-ray scattering is that the DDCS (the measured
quantity) is directly related to the dynamic structure factor S(Q, ),as shown
in equation 1.11. In fact S(Q, ) brings information about the dynamics of
the system in study, in the dierent branches of non resonant inelastic x-ray
scattering.
It is possible to optimize an IXS experiment, tuning the reciprocal mo-
mentum transfer Q
1
with respect the characteristic distances of the scatter-
ing electron system, l
c
(say the inter particle distance).
Thus one can, by looking at the magnitude of Q and , distinguish crudely
between four types of non resonant inelastic charge scattering experiments ,
a classication that is not only helpful as a guide to the signicance of infor-
mation brought by S(Q, ), but also denes the experimental requirements
[3]:
1. Scattering by valence electron density uctuations, or, in the sense of
the uctuation-dissipation theorem, by valence electron excitations, is
investigated with Qr
c
1 and
p
, where r
c
is the interparticle
distance and
p
the plasma frequency.
2. Scattering by inner-shell excitations (X-ray Raman scattering regime)
is investigated with Qa 1, E
B
, where a is the inner-shell orbital
radius and E
B
the binding energy of that orbital.
3. Scattering by collective ion excitations (phonons) is observed when
Qd 1,
ph
, where d is the interionic spacing (the space between
ions) and
ph
the phonon frequency.
4. The Compton scattering regime (Compton limit), where the electron
momentum density is the goal of the experiment. This regime is dened
by Qr
c
1, E
0
, where E
0
is a characteristic energy of the
system (binding energy for inner-shell states, Fermi energy for valence
electrons).
The experiment performed at ID16 for the present thesis project was
focused on the measurement of water molecular vibrational excitations and
d d excitations of NiO. In gure 1.2 the dierent regimes of non-resonant
IXS spectra are shown.
If the incident photon energy approaches the resonance condition (equa-
tion 1.17) the resonant part of DDCS, see equation 1.15 and 1.16, can be
higher by several orders of magnitude than the non-resonant part, and the
resonant inelastic x-ray scattering regime is reached. In this work only non-
resonant inelastic x-ray scattering is treated. So when we refer to IXS, in the
following we refer to non-resonant IXS.
1.2. Experimental aspects 11
Figure 1.2: Schematics of an excitation spectrum for Qr
c
1 (i.e. far from
Compton limit) [3].
1.2 Experimental aspects
As shown in section 1.1 the information about the dynamical structure factor
characterizing the uctuation of the electron density can be obtained by
measuring the double dierential cross section (DDCS). According to the
denition of the DDCS, the experimental scheme is clear: one has to prepare
a collimated monochromatic x-ray beam, whose ux and polarization state
should be known. The scattered beam must be energy-analysed and its
intensity is measured. The obtained spectral distribution of the scattered
radiation should be measured with the greatest possible signal-to-noise ratio
in the shortest possible time. Because of this experimental constraints the
development of the IXS technique had to wait the realization of the third
generation synchrotron centers, as the ESRF in Grenoble. This kind of source
are able to provide the necessary high brilliance for IXS experiments. The
brilliance is the most important aspect of the synchrotron radiation. It is
dened as the emitted number of photons per unit source size and divergence,
and per unit spectral width (0.1 % of the photon energy). The brilliance of
the most recent synchrotron radiation sources is higher by more than ten
orders of magnitude with respect to the rst synchrotron sources.
The general scheme of a synchrotron center is shown in gure 1.3.
Figure 1.3: Schematic representation of a storage ring with beamlines [12].
The electrons are accelerated by a linac and then by a circular accelera-
tor, called booster, reaching an energy of 6 GeV . After that the electrons,
divided in bunches, are injected in the storage ring, where they travel at rela-
tivistic speed for several hours. The system is designed to keep the electrons
energy almost constant.
The accumulation ring is composed of circular and straight sections. two
particular straight sections are necessary to supply to the electrons the energy
lost during the travel inside the accumulation ring. The electrons are injected
in bunches and their motion is synchronized with the electric eld inside the
radio frequency cavities of the accumulation ring. The total current inside
the ring depends on the number of bunches travelling. The higher level of
current (at ESRF 200 mA) is present when the synchrotron works in uniform
mode.
The accumulation ring of the ESRF synchrotron is composed of 32 sec-
tions. All these sections have the same magnetic structure. From every
sector is possible to obtain two radiation beams: one produced by the Bend-
ing Magnet (BM), and one by an Insertion Device (ID). The main goal of
the ID is to increase the brilliance respect the one available at a BM.
The x-ray source of the ID16 beamline is an insertion device. The source
is composed of three linear undulators with a magnetic period of 35 mm, a
maximum magnetic eld of 0.7 T and a length of 1.6 m, for a total length of
4.8 m [13].
An undulator consists of a periodic structure of dipole magnets (see gure
1.4). The static magnetic eld is alternating along the length of the undulator
with a wavelength
u
. Electrons traversing the periodic magnet structure
are forced to undergo oscillations and thus to radiate energy. The radiation
produced in this way is very intense and concentrated in narrow energy bands
in the spectrum. It is also collimated on the orbit plane of the electrons. The
synchrotron light is emitted at every magnetic pole, and its constructive
interference produces sharp peaks in the spectrum, called harmonics.
It is possible to change the energy of the photons in these harmonics,
simply changing the distances between magnetic poles. At the ID16 beamline
this distance can change from 12 mm to 35 mm [13], and it is possible to
choose energies inside the range 5 30 keV .
The angular divergence of the X-ray beam, produced by the undulators,
Figure 1.4: Schematic representation of an undulator. 1: magnets, 2:
electron beam, 3: synchrotron radiation. The electron beam wiggles with a
small deviation angle. As a result, ultra-bright and quasi-monochromatic light
is obtained by the interference eect.
is about 20 rad vertically and about 40 rad horizontally , with an energy
width of (E/E) 10
2
, and an integrated power of 200 W.
1.2.1 The IXS spectrometer
The experimental strategy used for IXS is a triple axis spectrometer, see
gure 1.5. First of all the beam coming from the undulator impinges the
monochromator crystals (1
st
axis, gure 1.5), to set the incident energy. Then
this beam coming from the monochromator hits the sample (2
nd
axis). The
third axis is at the analyser which selects the scattered energy by the sample,
the beam coming from the analyser is collected by the detector to measure
the intensity at xed energy.
A more detailed description of the spectrometer at ID16 beamline is in-
troduced in section 2.2.
Figure 1.5: Schematic representation of a triple axis spectrometer. The rst
axis is at the monochromator, the second one is at the sample and the third
one is at the analyser. Often in this work we refer to this kind of spectrometer
as the one analyser or single pass spectrometer.
1.2.2 Energy band-width
The energy selection by the monochromator and the analyser, uses the Bragg
reection from a Si crystal. The Bragg condition for the diracted intensity
maximum is given by:
2d
h
sin
B
= (1.19)
where d
h
is the distance between two planes of the family identied by
Miller indices (hkl), is the wave length of the diracted beam and
B
is
the Braggs angle. In gure 1.6 a graphical sketch of the Braggs diraction
process is reported.
Figure 1.6: Bragg diraction. Two beams with identical wavelength and
phase reach a crystalline solid and are scattered o two dierent atoms within
it. The lower beam traverses an extra length of 2d sin
B
. Constructive in-
terference occurs when this length is equal to an integer multiple of the wave-
length of the radiation.
Once a particular order of diraction is chosen, the relative energy reso-
lution
_
E
E
_
h
is an intrinsic property of the crystal, and it is inversely pro-
portional to the number of planes involved in the diraction process. As a
matter of fact, using the Dynamic theory of X-ray diraction, it is possible
to calculate the width[14][2]:
_
E
E
_
h
=
4r
e
d
2
h
V
b
C |F
h
| e
W
(1.20)
In the last equation r
e
is the classical electron radius, V is the volume
of the unit cell, C is the polarization factor, b is the asymmetry factor, e
W
the Debye-Waller factor (i.e. the temperature factor), and |F
h
| is the crystal
structure factor.
Equation 1.20 can be written introducing the extinction length t
ext
:
t
ext
=
V
2d
h
r
e
C |F
h
|
(1.21)
In this way the width becomes:
_
E
E
_
h
=
2d
h
bt
ext
e
W
(1.22)
The quantity t
ext
is dened as the penetration length of a beam inside
a perfect crystal, in the perpendicular direction to the diraction planes,
corresponding to an 1/e decrease of the incident beam intensity.
The resolution increases as the order of reection increase and it is in-
versely proportional to the extinction length and so to the number of planes
involved in the reection process.
An important limitation to the resolution comes from the photoelectric
eect which limits considerably the radiation penetration in the crystal. For
this reason, the attempt to improve the resolution power by simply increasing
the order of the reection and then the extinction length, has to satisfy the
condition that the absorption length has to be larger than the extinction one.
In gure 1.7 a comparison between the extinction length and the absorp-
tion length vs Q
h
. From this gure the two quantities become comparable for
Q
h
30

A
1
. For lower values, i.e. for low reection orders, the extinction
length is always smaller than the absorption one. For higher orders,then, the
ideal resolution power cannot be reached because the theoretic penetration
length inside the crystal is limited by the photoelectric absorption length.
Figure 1.7: Absorption length and extinction length vs photons momentum,
for Si.
Another important limitation to the resolution power comes from the
presence of imperfections and impurities inside the crystal. The denition of
a perfect crystal is connected to the considered reection order. It is possible
to approximate a crystal to a perfect crystal if the relative distance d/d,
between the lattice planes, is smaller than the intrinsic energy resolution of
the corresponding reection, i.e.:
_
d
d
_
_
E
E
_
h
10
8
(1.23)
From the experimental point of view, there is always the problem to
choose the right compromise between increasing the resolution and losing
reected intensity.
1.2.3 Quasi-backscattering geometry
The backscattering geometry is dened for
B
= /2. This conguration al-
lows using eciently the photon beam, at the same time reducing to the min-
imum the geometrical contribution to the total resolution of the instrument.
Of course it is impossible to realize experimentally the exact backscattering
geometry, but it is possible to approach it reaching congurations with
B
very near to /2. This kind of congurations is called quasi-backscattering
geometry.
It is possible to obtain a general expression for the energy resolution,
simply dierentiating the Braggs law 1.19, which we can write as:
2k cos
0
=
h
(1.24)
where
0
=
_
2

B
_
is the angle with respect to the normal direction,
i.e. the o-backscattering angle, k = 2/ is the wave vector of the incident
photon, and
h
= 2/d
h
is the vector of the reciprocal lattice.
The wave vector, in equation 1.24, depends on
0
and
h
; to every varia-
tion of these quantities a variation of k will follow, to be more precise:
_
k
k
_
=
_
k
k
_
2
h
+
_
k
k
_
2
o
(1.25)
From the energy expression in the case of a photon beam, E = ck, it is
possible to obtain:
_
E
E
_
=
_
k
k
_
(1.26)
Then using these last two equations:
_
E
E
_
=
_
E
E
_
2
h
+
_
E
E
_
2
o
(1.27)
The
_
E
E
_
h
term, in equation 1.20, can be written as:
_
E
E
_
h
=
D
cot
B
(1.28)
where
D
is the Darwin width (often expressed as ), and it represents
the angular acceptance of the considered Bragg reection. This quantity is
related to the nite energy resolution, and it corresponds to the angular range
where the Bragg reection occurs, i.e. the angular range where the photons
are eciently reected by the crystal.
The second term in 1.27 it is obtained dierentiating equation 1.24 with
respect to
0
, obtaining:
_
E
E
_
0
=
0
tan
0
=
0
cot
B
(1.29)
and performing some substitutions:
_
E
E
_
= cot
B
_
2
D
+
2
0
(1.30)
To obtain a resolution comparable with the intrinsic resolution of the
considered reection, the Darwin width has to be larger than the angular
divergence of the incident photon beam. For example, for an angle near /4
D
10 nrad, while the typical divergence of an X-ray beam produced by
an undulator is in the rad range. To set an optimal value for the Darwin
width, it is necessary to tune the Bragg angle; in fact using relation 1.28, one
can obtain:
D
=
_
E
E
_
h
tan
B
(1.31)
So to obtain a high angular acceptance and so a high energy resolution,
it is necessary to work near to backscattering.
1.2.4 Energy scan
The energy scans can be performed in two ways:
Changing the Bragg angle, as the scattered beam energy depends on
the diraction angle, as pointed out in equation 1.19;
Varying another parameter of the Braggs law.
The d
h
parameter, for example, is the distance between the lattice planes.
As a matter of fact it is possible to vary d
h
and select a specied wave length
simply changing the crystal temperature. In particular, a T modication
of the temperature induces a change of the lattice parameter:
_
d
d
_
= (T)T (1.32)
where (T) is the coecient of thermal expansion, in the Si case (T) =
2.56 10
6
.
From the Bragg law, E = hc/2d sin
B
, with xed
B
, it is possible to
obtain:
_
E
E
_
=
_
d
d
_
= (T)T (1.33)
This relation underlines the equivalence between the two energy scan
strategies.
1.2.5 Spherical Crystal Analyser
The scattered photons are collected by a horizontal spectrometer, that can
rotate around the sample position in order to select the scattering angle
and so the momentum transfer Q. At one extremity of the spectrometer an
analyser is xed. In this way, changing the value of the scattering angle and
performing an energy scan, the energy spectrum is obtained. The spectrom-
eter is designed following the Rowland circle geometry conguration. In
this conguration the sample, the analyser and the detector lie on the same
circumference, and the analyser is able to focus the scattered X-rays on the
detector. In fact spherical shaped analysers are used, with the radius of cur-
vature equal to the diameter of the Rowland circle. In gure 1.8 the Rowland
circle geometry conguration is shown.
Figure 1.8: Rowland circle geometry based x-ray spectrometer. The Row-
land circle diameter equal to the radius of the spherical crystal analyser.
To perform the energy analysis of the photons emerging from the sample
in a xed solid angle, Bragg reection from a spherical analyser in backscat-
tering geometry can be used. The spherical analyser gathers x-rays from
the sample, the source of the secondary waves, selects the photons in a nar-
row energy band, and delivers them to the focal point where the detector
is placed. However, bending introduces elastic strain in the crystal wafer,
which immediately deteriorates the intrinsic energy resolution of the Bragg
reection. To minimize the energy broadening due to the strain, dicing of
the silicon wafers into small cubic segments can be considered.
Dierent techniques are available to realize spherical crystal analysers.
For example the crystal segments can be glued on a spherical substrate, or
on a planar substrate, which is dynamically bent to a spherical shape with a
given radius [2].
An important condition that the spherical analysers have to satisfy is that
the size of the cubes, c, has to be much smaller than the focusing radius R
(c R). If this condition is satised the variation of the Bragg angle owing
to the presence of the dices is almost zero (c/R).
If the dimension c is chosen in order to keep the ratio c/R equal or smaller
than the Darwin width, the analyser reects the beam preserving the same
energy resolution. The nite size of the cubes gives anyway a contribution
to the total energy resolution, which is given by
E
E
=
_
c
R
_
cot
B
(1.34)
The analysers used during the experimental session discussed here, are
composed of 12000 Si dices, with dimensions 0.67 0.67 mm
2
and 3 mm of
thickness glued on a spherical Si substrate, with a radius of curvature R 1
m. In gure 1.9 a spherical Si diced analyser is shown.
Figure 1.9: Spherical Si diced analyser.
1.3 Double pass spectrometer
The IXS technique is used to probe the dynamics of dierent physical sys-
tems, such as the collective dynamics or the electronic excitations. The mea-
sured intensity is of course the convolution of the DDCS with the instrumen-
tal function. If this latter contribution is too broad, the physical information
which is looked for gets lost. So it is important to realize spectrometers of
good performance, and to minimize the width of their instrumental function.
The quality of a spectrometer depends on its capability to reveal and
eciently measure the DDCS of interest. It is possible to determine the
quality of a spectrometer simply looking at instrumental function, that is its
response for a very narrow spectrum. For a spherical crystal analyser this
resolution function is roughly Lorentzian shaped and it is possible to dene
some parameters that can summarize its properties.
Naturally the kind of physical processes observable using a particular
spectrometer is determined by its characteristic properties.
Two important parameters are:
1.3. Double pass spectrometer 25
FWHM - It is the Full Width at Half Maximum and it indicates the
resolution power of the spectrometer. As the FWHM increases the res-
olution power decrease. So reaching smaller FWHM values corresponds
to improving the resolution power of the spectrometer.
Contrast (C) - It is the ratio between the intensity at zero exchanged
energy and the intensity in the tails of the resolution function.
These two quantities determine roughly the shape of the resolution func-
tion. In synthesis the FWHM tells how much rapidly the instrumental reso-
lution function decreases near the central peak, while the contrast measures
how fast it decrease on the tails of the function.
Many eorts have been carried out to minimize the FWHM and obtain
a good contrast, as example using higher orders for the Bragg reection for
the monochromator and the analysers.
In this Thesis work another root to improve the instrumental resolution
was carried out. This attempt consists in changing the geometry of the IXS
spectrometer, simply adding a second analyser just after the rst already
present in the classical IXS spectrometer design. The goal of this set-up is to
select with more precision the energies scattered by the sample and revealed
by the detector.
This system, also called double analyser spectrometer, could be thought
as a spectrometer with four axis elements, as it is shown in gure 1.10.
When multiple-crystal diraction occurs, the resulting resolution function
is the product of the two analysers (crystal) resolution functions[2]. So the
resulting resolution function will be:
f
tot
= f
1
f
2
(1.35)
Figure 1.10: Schematic of a spectrometer with four axis elements. The rst
axis is the monochromator, the second one is the sample, the third one is the
rst analyser, and the fourth the second one. The analysers are followed by
the detector. Often in this work we refer to this kind of spectrometer as the
double analysers or double pass spectrometer.
1.3. Double pass spectrometer 27
where f
1
and f
2
are respectively the resolution function of the rst and
of the second analyser. As it will be shown in the following chapters, this
corresponds to a slight reduction of the total FWHM, and more importantly
to an improved contrast.
Chapter 2
The experiment
2.1 ID 16 beamline at the ESRF
ID16 is an undulator beamline dedicated to high and very high resolution
inelastic X-ray scattering (IXS) [8]. This technique allows both the energy
and the momentum transfer to be controlled in rather wide regions, which
makes it possible the study of quite distinct physical (and chemical) problems
in condensed matter, including vibrational molecular excitations as well as
valance and core electron spectroscopy, see Chapter 1.
The beamline is basically composed of four experimental hutches and
three control cabins (see gure 2.1). These hutches have dierent functions.
The rst hutch, OH1, contains the primary slits, a set of collimating
beryllium lenses, an attenuator unit, and the white-beam shutter. The un-
dulator beam is then transferred through the experimental hutch, EH1, in
a lead enclosed vacuum tube to the hutch OH2, where the high-heat load
Si monochromator is located. Here the beam is premonochromatized to a
bandwidth E/E 2 10
4
using a pair of independent Si(1, 1, 1) crystals.
Such crystals are mounted on a rotation stage and are cooled using liquid
30 2. The experiment
nitrogen to evacuate the heat load of the undulator beam [1].
After the pre-mono it is possible to mount a post-monochromator, for an
optional, additional monochromatization
1
. Also there is a chamber with two
mirrors after the post-monochromatization stage. The two mirrors can be
alternatively used. The rst one focuses the beam on the sample position,
located in the following hutch (MH1), to a spot of 120 50 m
2
(H V ).
The second mirror focuses the beam only in the horizontal direction, while
it collimates it in the vertical one to a divergence of 4 rad. In the same
hutch, the premonochromatic-beam shutter (SS2) allows to access the follow-
ing hutch MH1 while keeping the beam on the premonochromator. In MH1,
an optical table is available for the installation of various optional compo-
nents, followed by the sample stage. This stage is usually equipped with a 1
or 2 m long horizontal spectrometer used for IXS and XES experiments[1].
The control cabin CC1 contains the motors and the computers (PCs)
used to control the experiment and the entire beamline.
The EH1 is also used for IXS experiments with meV resolution, but it
was not used to build the double analyser spectrometer.
2.2 Spectrometers
The spectrometers presented in this work are designed for non-resonant IXS
(see Chapter 1).
The traditional system, used to perform IXS measurements (see section
1.2.1), consists of a single analyser spectrometer, see Figure 2.5.
In this section the experimental set-up is presented , as it was used during
1
To give an idea of the monochromatization capabilities of the post mono, it is capable
to produce an energy width of 40 meV, in case of (4,4,4) reection, and to give an energy
width of 15 meV, in case of (5,5,5) reection
2.2. Spectrometers 31
Figure 2.1: Beamline layout scheme.
the test. Two dierent congurations of the spectrometer have been used to
perform a comparison: the single pass spectrometer (see Section 2.2.1) and
the double one (see Section 2.2.2).
The spectrometers were mounted on a table rotating around a central
axis, useful to dene the scattering angle, and to choose if we want to work
in transmission or in reection mode.
The table is equipped with a goniometer in order to measure the scatter-
ing angle, dening the direction we chose to measure the scattered radiation
(schematic representations in Figure 2.2 and 2.3, while a photo of the exper-
imental set up is shown in gure 2.4), .
The analysers, the detector and the sample are motor controlled. Each
motor is in turn controlled by the control room PCs.
The analysers have four degrees of freedom: the ath angle between the
normal to the analyser and the vertical direction is really important to x the
right Bragg angle and for the alignment procedure; the movement along the
straight line connecting the sample to the analyser (ax direction) is useful
to x the distance between the two analysers or between the sample and the
analysers (then this degree of freedom is really important to optimize the
focus); the az height movement is useful for the double pass alignment and
Figure 2.2: Schematic representation of the experimental set up. View from
the top.
to maximize the intensity; the movement along the normal direction to the
last two ones is called ay.
The sample has six degrees of freedom: the movement along three Carte-
sian axis (x,y and z called sx, sy and sz ), and three angles (, , , called
Sth, achi, a).
The detector has three degrees of freedom: the movement along the
distance between the two analysers detx; the height detz; APDrot, which
is the angle between the normal to the detector and the vertical direction.
2.2.1 Spectrometer in single pass
In the single pass mode (i.e. the case of a single analyser spectrometer), the
x-ray beam, focused on the sample by a focusing mirror, hits the sample (see
gure 2.5). A portion of the scattered rays is collected by the spherical silicon
Figure 2.3: Schematic representation of the experimental set up. Frontal
view.
analyser, that focuses the scattered radiation on the detector. The purpose of
this analyser is not only to focus the rays onto the detector surface, but also
to select the interesting energies for the experiment. To reach this goal the
analyser works in Bragg reection (see section 1.2.2) in quasi-backscattering
geometry (i.e. with an angle near zero, when it is dened between the incident
and the direction normal to the surface). For more details see section 1.2.3.
In gure 2.6 [6] the schematic design of the single pass spectrometer is shown.
In order to reduce the noise due to the scattering of air, 2 vacuum cham-
bers in single pass mode and 3 in the double pass mode have been mounted.
The 1
st
chamber is the Sample Chamber, containing and surrounding the
sample. The 2
nd
one is the rst analyser chamber, it envelops the x-ray path
from the sample chamber to the rst analyser. The 3
rd
chamber (used only
in the double pass mode) is the second analyser chamber, that covers the
x-rays path from the sample chamber to the second analyser and from it to
the detector. These chambers are made of aluminium and steel which are not
transparent materials for the x-rays. For this reason in these vacuum cham-
bers there are some windows, along the x-rays path. In order to maintain the
vacuum, these windows are closed by Kapton foils, almost transparent for the
Figure 2.4: Photo of the experimental set up, inside the MH1 (experimental
hutch). In particular note the rst analyser vacuum chamber (on the left),
the second analyser with its vacuum tube (on the right) and the sample (in
the center).
Focusing
Mirror
Pre - Monochromator
Undulator
source
White beam
Premonochromatic
beam
0 m 48 m 52 m 54 m 56 m 58 m 60 m 62 m 64 m 66 m 50 m
Monochromatic
beam
Post
Monochromator
Sample
Maxipix
Detector
Spherical
analyzer
crystals
R.C. = 1 m
Multiple-analyzer
crystals spectrometer
Figure 2.5: ID16 beamline conguration for the single analyser spectrome-
ter.
Figure 2.6: Single pass spectrometer schematic design, dimensions in mil-
limetres [6].
X-rays. The analyser, for the rst pass, is mounted inside a nine analysers
chamber, see gure 2.7. In the conguration used for this experiment, only
the central analyser was used.
The analysers are composed of cubes, with dimensions 0.67 0.67 mm
2
and 3 mm of thickness glued on a circular Si substrate, obtained by dicing a
silicon wafer. How explained before, in section 1.2.5, the reason of the dicing
is that bending the wafer would introduce elastic strain in the crystal, which
would immediately deteriorate the intrinsic energy resolution of the Bragg
reection[1].
The principal defect of the single pass spectrometer is to have a quite high
Figure 2.7: Analyser chamber. Only the central analyser was used.
level of intensity in the tails of the resolution function, which means that in
this conguration the system has not a good contrast (see section 1.3). This
eect can hide some physical information about the system in analysis.
2.2.2 Spectrometer in double pass
The intensity of tails in the experimental resolution can be reduced by using
a second analyser, installed just after the rst one (see gure 2.8).
In this kind of system, called double pass spectrometer, the rst part
of the set-up as the same as explained before, with the only dierence that
the rst analyser does not focus on the detector directly, but just above the
sample chamber. After that the rays hit the second analyser focusing on
the detector. In this way, there is a two step selection in energy, one by the
rst analyser and the other by the second one. At the end the resolution
function is the convolution of the product of the resolution functions of the
two analysers with that of the monochromator (f
an
f
mono
).
2.3. Detector unit 37
The distance between the analysers is two meters. So the distance be-
tween every analyser and the center of the spectrometer is 1 m, equal to the
analysers radius of curvature. The diameter of every analyser is 100 mm,
but a circular slit with an inner diameter of 80 mm is used, to cut away the
contribution from the border of the analyser, that has some imperfections.
The radius of curvature, of the inner surface of the analysers is 100 cm.
Focusing
Mirror
Pre-Monochromator
Undulator
source
White beam
Premonochromatic
beam
0 m 48 m 52 m 54 m 56 m 58 m 60 m 62 m 64 m 66 m 50 m
Monochromatic
beam
Post
Monochromator
Sample
Maxipix
Detector
Spherical
analyzers
R.C. = 1 m
Double-analyzer
spectrometer
Second
Analyser
First
Analyser
Figure 2.8: Double pass spectrometer scheme.
The system was designed in order to minimize the path through the air
for the x-ray beam. To achieve this goal a vacuum tube was xed to the
table, covering the x-rays path from the center of the table to the second
analyser (see Figure 2.4).
2.3 Detector unit
The detector used is a Maxipix detector (Multichip assembly for X-Ray imag-
ing based on a photon counting pixel array)[15]. This device is based on
the Medipix2 ASIC (Application-specic integrated circuit), whose schematic
representation is shown in gure 2.9 [16]. The system achieves 1 kHz frame
rate (with one Medipix2 chip), 290 microseconds readout dead time, noiseless
(photon-counting) detection. It consists of 256 256 pixels each of 55 55
m. The thickness of the active Si layer is 500 m.
Using a position sensitive detector oers several advantages compared to
a point detector, as it will be shown in the following section.
Figure 2.9: Schematic representation of the CMOS pixel read-out chip,
working in single photon counting mode[16].
As for every part of the spectrometer, the detector is also a modular unit
that can be replaced by other types of detectors if necessary[6]. The detector
was not in vacuum but just after the last Kapton foil, closing the second
2.4. Experimental methods 39
analyser vacuum tube.
2.4 Experimental methods
The main procedures used during the experiment, starting with the mount-
ing and calibration of the apparatus and ending with the data collection
procedures, are presented in this section.
2.4.1 Alignment and focusing
The alignment procedure consists in aligning every part of the spectrometer
along the optical axis, in order to control the direction of the x-ray beam and
to maximize its.
The rst part of the alignment (the rough one) was made, during the
installation, using a laser and two bent analysers (without dicing to maximize
the visible light intensity) (see Figure 2.10).
The rough alignment procedure was iteratively repeated until a good level
of alignment was reached. It basically consists of three steps:
Putting the analysers and the sample on the same straight line.
Setting the center of rotation of the table on the sample.
Setting the zero for the angle of incidence on the analyser (dened with
respect to the normal to its surface).
In the rst phase of the rough alignment the laser was put below the
second analyser pointing to the rst one. In place of the sample a tip was
mounted. The direction of the laser beam and the position of the analysers
were adjusted in order to hit the tip and the center of the rst analyser
with the laser. As it is shown in the gure 2.10, the red spot of the laser
was pointing to the center of the analyser, passing through the tip, in this
way we were sure that the two analysers and the tip were lying on the same
straight line.
In the second phase we had to verify whether the sample was in the center
of rotation of the goniometer.
After this operation there was the last phase in which the rough alignment
was controlled again and in particular we veried that the two spots (one
direct and one reected by the rst analyser) were overlapping on the sample
tip. When the two spots were overlapped we dened the zeroof the analyser
ath angle. During the installation and the alignment the analysers were put
at a distance of 1000 mm. In this way the rays coming from the 1
st
analyser
focus just upon the sample chamber, and those coming from the 2
nd
one focus
on the detector surface, see gure 2.11.
This rough alignment and focusing procedures were also performed for
the 2
nd
analyser just using as source the reected laser beam from the rst
analyser. At the end we dened the zero for the angle of incidence both for
the rst and the second analyser.
We then chose a Bragg angle of 88.5
(i.e. 1.5
with respect to the normal),

that is compatible with the monochromator used in this set up phase. As
a matter of fact, the monochromator selects the energies by the Braggs
reection law (see section 1.2.2). To maximize the intensity the spectrometer
needs to be congured so that both monochromator and analysers select the
same energy, i.e. they need to work with the same Bragg angle. We used
a channel cut monochromator (see gure 2.12), this kind of monochromator
has a limit in the Bragg angle at which can be operated without blocking the
beam, in the particular case of the monochromator used in this experiment
(a) (b)
(c)
Figure 2.10: Alignment procedure. The image 2.10a shows the laser below
the second analyser, image 2.10b shows the laser on the tip (at the sample
position) and 2.10c one is the laser incident on the rst analyser.
Figure 2.11: Focusing, schematic representation.
the limit is near to 88.5 88.8 degrees for the Bragg angle.
Figure 2.12: Channel cut schematic representation on the left and a picture
of a couple of channel cut crystals on the right.
Another constraint for the accessible Bragg angles comes from the geom-
etry of the spectrometer. As a matter of fact we had to be sure that the
rays coming from the rst analyser (in the gure it is called

b
) and directed
to the second one were not blocked by the detector mount or by the sample
chamber.
In this way the distance between the two beams passing through the
center of the spectrometer, is of 52 mm, which corresponds to a Bragg angle
of 88.5 degrees.
In order to pass to the next alignment phase, using the x-ray beam, the
analysers in the spectrometer were changed , using the diced ones. After that
the rough alignment was veried by the laser.
A little sticky tape was put at the sample position, inside the vacuum
sample chamber, at the top of the tip. This little piece of tape is useful
because it scatters the x-ray beam in all directions.
To be sure that the x-ray beam hits the target a telescopic sight was used.
We put an x-rays sensitive paper on the position of the sample, after an x-
ray exposure of few seconds, it was possible to understand exactly where the
beam was hitting. So we knew exactly where to put the sample to be hit by
the x-ray beam.
To obtain the resolution curve the undulators were optimized to obtain a
range of energies around 7910.9 eV. Moreover we aligned the pre- and post-
monochromator to select the same energy, that corresponds to a scattering
angle of 88.5 degrees. We chose to work at this energy because we started the
experiment using the (4,4,4) reection planes family, which in backscattering
conguration selects the energy of 7908.2 eV. By means of Braggs law, it is
possible to calculate the energy of the intensity maximum, o backscattering.
We obtained the value 7910.9 eV for an angle of 88.5 degrees.
After that, modifying the position of the analyser (the angle ath1 and the
ax1 analyser position) and the position of the detector we found the reected
x-ray beam from the rst analyser. Then we started to search the reection
on the second analyser, with the same procedure.
Once we found this second reection we started to optimize the focus of
the x-ray beam coming from the Optical Hutch 2 on the sample (see gure
2.1). To do this we unmounted the sample chamber and the detector, and
we put a CCD detector with a phosphorus screen on the sample position.
Varying the focusing mirror position, the intensity distribution on the
detector changed, becoming sharper when the system was closer to the best
focusing conguration.
During the experiment, everytime we made any scan in energy varying the
incident x-ray beam energy, we changed the Bragg angle of the channel cut.
As it was shown in gure 1.6, when Bragg reection occurs, the incidence
angle of the incident beam is equal to the exit angle of the beam. Because of
this change in angle, also the intersection point of the beam with the sample
changes. So the scanning Bragg angle of the monochromator corresponds to
moving the beam position at the sample.
Because of this, the sample has to follow the beam. For this reason it
was necessary to perform a calibration procedure. To carry out it, we left
the CCD detector at the sample position, we varied the energy selected by
the monochromator, and varied the height of the table to follow the beam
(i.e. in such a way to see the beam image acquired by the CCD always at
the same position). In this way before every measurement we were sure that
the x-ray beam was hitting the target.
After this tracking procedure we unmounted the CCD detector, and we
mounted the sample chamber and the MAXIPIX detector. We started to
optimize for the best focus for the analysers. We carried out this procedure
for both congurations of the spectrometer and, as usual, we started with
the single analyser and ended up with the double one. Furthermore the
best focus research was repeated for any modication of the experimental
apparatus (for example changing analysers). To achieve this goal we made
some energy scans (a4scan, see section 2.4.2) for dierent congurations of
the system (i.e. varying the x position of the analysers and of the detector,
i.e. varying the focal distance), and we calculated the FWHM of the image
on the detector for every scan. At the end we chose the conguration with
the best FWHM.
2.4.2 Data collection and Compensation
To characterize the spectrometer we performed measurements of three dier-
ent kinds. At the beginning we started to analyse the resolution curve of the
double analyser spectrometer and to compare this resolution with the single
pass one. After that, we collected data for two dierent samples (nickel oxide
powder and water), whose excitations are interesting to test the performance
of the system. For every kind of measurement we performed two dierent
kind of scans, based on two dierent macros:
1. a4scan.
2. dzscan.
The a4scan macro collects the data varying the incoming energy and
saving the images registered by the Maxipix detector. These kind of scans
are performed in the inverse geometry, where the incident photon energy
E
1
= E
2
+ is scanned, observing scattered intensity at a xed photon
energy E
2
. This kind of geometry has the advantage of a constant eciency
of the spectrometer throughout the energy scan [6]. In synthesis, during the
a4scan the undulator conguration is xed, and the macro performs dierent
operations at the same time. First of all the selected energy changes, and
so do the Bragg angles of the pre-monochromator and post-monochromator;
moreover the height of the focusing mirror also changes to follow the non-xed
exit of the post-monochromator and nally the height of the table changes
to keep the beam on the sample position. Of course, at each energy step
the a4scan macro acquires and stores the image collected by the MAXIPIX
detector.
The dzscan macro, instead, works at xed incoming energy, and simply
scans the height (dz) of the detector. This height change corresponds to an
energy variation, because of the Braggs Law = 2d
H
sin
B
.
In fact every height modication corresponds to a variation in the Bragg
angle (see gure 2.13). In this way the dzscan performs an energy scan
without changing the incoming energy. This means that this kind of scan is
faster than the a4scan, because the dzscan moves only one motor (dz, i.e.
the height of the detector).
dz
detector
x ray reflected
at different
Bragg angles
with different energies
Silicon
spherical
analyser
incindent x rays
Figure 2.13: dzscan concept.
The main limit of the dzscan is that, because of the angular acceptance
of the crystal analyser, the range of the energies cannot be too wide
2
. On
the contrary the a4scan can span a wider energy range than the dzscan, but
it is also consuming more time, since it changes the monochromator angle,
the focusing mirror and the sample height.
The a4scan was the most used type of scan. To reach a better resolution
we used a procedure called compensation, that uses the same idea of the
dz scan on the data collected by the a4scan. As already seen in Chapter
1, the analysers are diced, to prevent the bending of the Si wafer, that can
introduce elastic strain in the crystal (see section 1.2.5). The nite cube size
adds a contribution to the energy resolution in the single pass conguration,
which is given by
E
E
=
_
c
R
_
cot (
B
) (2.1)
where c is the length of the cube edge, R is Rowland circle diameter (and
also the bending radius) and
B
is the Bragg angle.
This contribution in the double pass case becomes:
E
E
=
_
c
2R
_
cot (
B
) (2.2)
The reduction by a factor of two is due to the double optical path length
in the double analyser spectrometer with respect to the single one. In fact
the scattered rays from the sample travel for 2R to reach the detector in the
DP conguration, while in the SP the length of the optical path is simply R.
The compensation procedure, developed by the ID16 team, is useful
to eliminate this contribution, utilizing a two-dimensional position-sensitive
2
For example in a backscattering geometry with a (4,4,4) reection, the angular accep-
tance is = 2190 rad, which corresponds to an energy range of E = 39.3 meV
pixel detector, see in this chapter section 2.3 [6].
The Maxipix detector, as already shown in section 2.3, is composed by
pixels 55 m wide. The compensation macro exploits this structure and
performs a dispersion-compensation correction to the data recorded by the
individual pixels.
If we consider a point source, the focus of a diced analyser is a square with
dimensions given by the size of an individual cube magnied by a factor of
two. Only the image of a single cube is seen, since the images of all cubes are
all superimposed to a good approximation. In gure 2.14 the image, acquired
by the detector for the single analyser spectrometer operation, shows that
the image produced by the spherical diced analyser is a square obtained by
the superposition of all cubes composing the analyser.
Figure 2.14: Image acquired using the single analyser spectrometer and
using the Si(444) reection. This image shows that the image produced by
the spherical diced analyser is to a good approximation the superposition of
all cubes images.
Along the z direction (i.e. the vertical direction on image 2.14) the Bragg
angle on the analyser varies. A Bragg angle variation corresponds to a change
in energy, and if the analysed radiation is detected with a position insensitive
detector, this variation contributes directly to the resolution function, with
the contribution described by equation 2.1.
However, if both the source and the detector lie on the Rowland circle,
the radiation reected with a specic Bragg angle by the cube is observed in a
specic position in space in the focus. That is, there is a clear correspondence
of position and energy for the collected x-rays [1]. So if we consider every
single stripe of the detector pixels, for every stripe we have a dierent energy.
In this way, a second selection in energy can be performed, thus improving
the resolution.
The basic idea of the compensation procedure is to obtain several resolu-
tion curves, one for every horizontal line of pixels of the detector. After that
it is possible to shift and overlap all the curves, in order to obtain one curve
with higher intensity.
To reach this goal it was necessary to determine the
Energy
dz
relation, found
as the value
Energy
dz
for which the FWHM has a minimum.
In gure 2.15 [4] it is possible to see two measurements of the resolution
curve made by the ID16 team, showing the dierence between the PISD
(Position Insensitive Detector), i.e. not using the compensation, and the
PSD (Position Sensitive Detector), i.e. using the compensation. The results
show that the FWHM decreases from 190 meV to 27 meV, using the Si(555)
reection at 88.5
.
As a matter of fact, using the PSD the contribution of equation 2.1 to
the total width is now reduced to that reported on equation 2.3, where p is
now the pixel dimension, p << c, in fact in our case p is about 55 m, while
c is of 0.67 mm.
The contribution to the energy width in the single pass case, owing to the
pixel dimension, is:
E
E
=
_
p
2R
_
cot (
B
) (2.3)
While in the double pass case this contribution becomes:
E
E
=
_
p
4R
_
cot (
B
) (2.4)
where p is the pixel dimension, and R is the diameter of the Rowland
circle. Also in this case, a reduction of a factor two in the energy width takes
place. As it is shown by equations 2.1, 2.2, 2.3 and 2.4, another eect of the
double analyser spectrometer is that it decreases the geometrical contribu-
tions to the total energy width, further improving the resolution power.
Eect of Shielding
To shield the apparatus from air scattering we put a lead shield over the path
of the incoming x-rays, lead tape shielding around the detector and around
the analyser edge, and a beam stop on the rear of the sample chamber, as it
is shown in gure 2.16.
The eect of proper shielding is clear, in fact with this shielding we have
a background one hundred of times lower than without, as it is possible to
see in gure 2.17.
Figure 2.15: Results of data analysed using the position sensitive detector
(PSD), for the Si(555) reection at 9.9 keV . The dashed line represents the
resolution curve when all the pixels are summed. The solid line represents
the resolution function when the position/energy - dependence is taken into
account, and the images from the position sensitive detector are analysed by
summing over the pixels in the non dispersive (horizontal) direction. On the
left panel the resolution function for a series of lines of pixels is shown. On
the right image the nal result is shown, obtained exploiting the compensation
relation, i.e. translating and summing the data over the vertical direction.
[4]
Figure 2.16: Shielding on the spectrometer
600 400 200 0 200 400 600
10
5
10
4
10
3
10
2
10
1
10
0
10
1
Energy (meV)
I
n
t
e
n
s
i
t
y

a
r
b
i
t
r
a
r
y

u
n
i
t
s

double pass resolution without shielding
double pass resolution with shielding
Figure 2.17: Shielding eect on the background for the double analyser spec-
trometer. It is possible to see that the background, in the tails, was reduced
by a factor of 100. The spectra are normalized to the maximum.
Chapter 3
Ray tracing
One of the most important steps in this thesis work had the purpose of
predicting the response of the spectrometer, in order to optimize its best
conguration. Ray tracing represents the natural choice to reach this goal.
So the double analyser spectrometer was studied by ray tracing, varying its
parameters, and it was compared to the single analyser spectrometer. In this
chapter, the results obtained by ray tracing are presented.
3.1 X-ray ray tracing
In physics, ray tracing is a method for calculating the path of waves or
particles through a system with regions of varying propagation velocity, ab-
sorption characteristics, and reecting surfaces. Under these circumstances,
wave fronts may bend, change direction, or reect o surfaces, complicating
the analysis. Ray tracing solves the problem by repeatedly advancing ide-
alized narrow beams called rays through the medium by discrete amounts.
Simple problems can be analysed by propagating a few rays using simple
mathematics. More detailed analyses can be performed by using a computer
54 3. Ray tracing
to propagate many rays.
In the case of X-rays, the ray tracing needs to use not only geometrical
optics, but also x-ray optics rules (see Chapter 1) in particular taking into
account the dynamical theory of x-ray diraction.
The rst x-ray tracing codes were developed in 1992 by Homan et al.
[17]. In the last twenty years, x-ray ray tracing techniques were improved
reaching a high level of precision, to foresee the behaviour of x-ray optics.
Shadow is the software that was used to perform the ray tracing work.
3.2 SHADOW
SHADOW is a software package designed to study the propagation of a pho-
ton beam through an optical system. The program is general, but it is
optimized for the case of x-rays and reective optics encountered in the XUV
( eXtreme Ultraviolet Radiation, it can be produced for example by Soft X-
Ray Lasers) and in synchrotron radiation applications. The code is designed
to be simple and reliable, with prompt- and menu-driven programs.
SHADOW is composed by a core of main programs and by a collection of
utilities used to process the output from the main programs [18]. In particular
it is possible to present schematically the structure of the system dividing the
entire program in three groups. The rst group is used in the I/O session to
dene the characteristics of the source and of the optical system. The second
is the one performing the actual calculations, i.e. generating and tracing
the photon beam through the optical system. The third includes analysis
programs necessary to interpret the results of the calculations performed
earlier. The programs are run sequentially by the user in an interactive I/O
session; they can also be run in batch mode. At the ESRF it was possible to
3.2. SHADOW 55
use a GUI (Graphic User Interface) to work on Shadow, developed by the
Advanced Analysis and Modelling group of the ESRF. In this version it was
possible to set the variables by a very user friendly graphic environment.
SHADOW operates on an OPTICAL SYSTEM (OS), which is in turn
formed by a SOURCE and by (one or more) OPTICAL ELEMENTS (OE).
Figure 3.1 illustrates an OPTICAL SYSTEM, formed by two mirrors. The
solid line represents the central axis or optical axis; it connects the poles
of the mirrors and denes the backbone of the system.
The photon beam generated at the source is traced on the rst mirror to
the continuation plane(i.e. just after the OE), where an intermediate image
is generated. This image becomes the source for the next mirror and it is
traced through to the nal image position. SHADOW allows great exibility
in specifying the position and the type of mirrors used in the calculations.
Data les are generated at each critical position in the optical element,
i.e. before and after the element. In this way, many optical elements can
be concatenated together (up to 20). The les are automatically numbered,
i.e. a number is attached to the end of the le name, to keep track of what
belongs where.
The geometry used by the program is quite simple. SHADOW works in
a Cartesian reference frame, always using the full specication of the vectors
[19]. Most optical ray tracing programs refer the rays components to the
optical axis but, although cheaper in terms of storage, this solution limits
strongly the type of geometry which is possible to implement. SHADOW
denes a vector for each optical element. The geometry is dened by the
image shown in gure 3.2.
After dening the system geometry, i.e. the position of source, optical el-
ements and detector, Shadow needs the denition of the physical parameters
56 3. Ray tracing
Figure 3.1: Two-mirrors optical system [18].
Figure 3.2: Optical element geometry and continuation planes. In paren-
thesis, the le name of every component. [19].
3.3. X-ray ray tracing by SHADOW 57
to start a complete simulation.
In particular it is necessary to dene the physical properties of each ele-
ment. For example: the crystal type (such as Si or Ge), the set of plane used
for reection ((444),(555) and so on) and the relative energy, the Debye-
Waller factor, the shape of the source and the intensity distribution, the
shape of the optical elements and so on. To reach this goal the applications
supplied in the preprocessor of SHADOW are useful. This family of programs
permits to build the optical library les that SHADOW needs to perform the
tracing. Using the GUI, interacting directly with the les is not necessary
because they are passed automatically to the tracing program.
3.3 X-ray ray tracing by SHADOW
Before facing the experimental session, dierent simulations were performed
using the GUI SHADOW environment. The system was tested for several
congurations, trying to maximize the intensity.
3.3.1 Source
The SHADOW preprocessor supplies dierent kind of sources. In particular
it is possible to choose the shape of the source, the intensity, spatial distri-
bution, the divergence and the angle distribution of the beams, the energy
range and the energy distribution. The main available shapes are: punctual,
rectangular, circular and elliptical. These shapes are dened in the normal
plane to the optical axis and it is necessary to provide their spatial dimen-
sions in order to dene them, for example the length of the sides for the
rectangular shape or the lengths of the minor and major semi-axes for the
elliptical shape.
58 3. Ray tracing
Concerning the intensity distribution it is possible to choose between:
Uniform distribution, in which the density of rays is constant
Gaussian distribution, in which the density of rays decreases like a
Gaussian with the maximum on the center of the source
Conical distribution, in which the density of rays decreases linearly
from the center of the source
For the Gaussian distribution it is necessary to provide the widths
x
and
z
.
Another important variable is the angle distribution, i.e. the emerging
angle distribution of rays from the surface normal to the optical axis. This
parameter is very important because permits to dene the beam divergence
as well. In SHADOW dierent kinds of angular distributions are available, as
uniform, Gaussian, and conical. Concerning the angle distribution, once the
typology of the divergence is dened, SHADOW permits to provide dierent
values for the horizontal and vertical angular divergence.
The denition of the source ends with the declaration of the number of
rays inside the source, i.e. the absolute intensity of the source. This intensity
is equally spread inside the energy range by default, even if it is possible to
dene dierent kinds of distribution, like Gaussian, constant, etc..
In gure 3.3 an example of source used during the ray tracing tests is
shown. This is a source with a Gaussian spatial intensity distribution, ellip-
tical shaped, with a constant intensity vs energy distribution on the energy
range that was chosen. This source is composed of sixty thousand rays (the
intensity, in SHADOW, is dened in number of rays).
This source is similar to the ray beam used for the experiment. The
intensity vs energy distribution was chosen to be constant because we were
interested to understand the behaviour of the analyser without other eects
related to an energy distribution of the source. However the real source used
for the experiment was a Gaussian distributed source, with a very little .
The nal resolution function was then the convolution of the monochromator
response with the analyser one.
Figure 3.3: Typical Gaussian source generated by SHADOW with an inten-
sity of 60000 rays. This kind of source was generated also with a constant
energy distribution around the energy selected for the chosen reection, in
order to study the instrumental function.
3.3.2 Analysers
As shown in section 1.2.5, dierent kind of analysers are available.
Using the Shadow preprocessors it is possible to dene completely an OE.
The denition of an OE (Optical Element) is carried out in two steps:
60 3. Ray tracing
1. The geometrical structure is dened, i.e. the shape of the surface, the
distance from the source or from another OE and the angle of incidence.
2. The physical properties are specied, i.e. the material (Si or Ge), the
reection planes, the Debye-Waller factor etc.
Concerning the geometry of the system, the double analyser spectrome-
ter has both analysers on Rowland circles, in order to achieve simultaneous
focusing and analysis, see section 1.2.5. For this reason the bending radius
of the spherical analysers is equal to the Rowland circle diameter. Shadows
preprocessor supplies the user with dierent kind of surfaces for the analysers,
such as spherical, elliptical, toroidal and plane ones. The angle of incidence
to the OE is dened between the incident direction and the normal to the
surface (like it is shown in gure 3.4 ).
Furthermore Shadow gives the possibility to put a slit or a grating in front
of every optical element. For every OE it is also possible to view the footprint,
i.e. the illumination of the OE viewed from the top, with or without slits.
Figure 3.4: Spherical mirror in Shadow. The angle of incidence is dened
as that between the incident direction and the normal to the surface.
However the geometrical structure of the analysers used during the exper-
iment is more complicated. In fact it is obtained by the composition of little
and perfectly at cubes xed on a spherical surface. These little Si cubes [4]
are utilized in order to work with perfect crystal optics. Such a structure is
not automatically provided by the Shadow preprocessor, so it was necessary
to prepare a le with the description of this structure. To reach this goal
a Matlab program was written in order to generate the appropriate surface
le needed by the preprocessor. The resulting surface obtained by Matlab is
reported in gure 3.5. In this reconstruction the 0.13 mm groove between
two adjacent cubes is neglected.
Figure 3.5: Spherical diced mirror obtained by Matlab. The radius of cur-
vature is 100 cm, while the side length is 10 cm. The length of the dices is
0.67 mm. The axis names are the same as in gure 3.2.
62 3. Ray tracing
3.3.3 The optical system
Two congurations of the spectrometer were studied by ray tracing: the
single pass spectrometer (SP, Single Pass) and the double pass one (DP,
Double Pass). The Optical system was composed of one source, one image
plane and one OE (the analysers) for the single pass and two for the double
one. In gure 3.6 a brief representation of the optical system is shown, for
the case of the double analyser spectrometer.
Obtaining a resolution function with faster decreasing tails than that
obtained using the single analyser spectrometer is the main purpose of the
double analyser spectrometer. When multiple-crystal diraction occurs, the
resulting resolution function is the product of the two analysers resolution
functions[2]. The resolution function of a single analyser is approximatively
a Lorentzian function. Therefore the most important gain is in the contrast
of the double analyser spectrometer, expected to be higher than in the single
pass spectrometer. The contrast is a measure of how fast the tails of the
resolution function decrease on increasing energy. To have a quantitative
evaluation of the contrast a possible denition is:
C =
I(0)
I(20)
(3.1)
where the I(0) is the intensity at the elastic peak (i.e. 0 eV Energy
transfer) and I(20) is the intensity at 20 from the elastic peak (i.e. for an
energy transfer of 20).
At the same time this improvement in contrast corresponds to an intensity
loss on an absolute scale. Estimating the value of this loss, and calculating
the luminosity of the system, was another goal of the ray tracing analysis.
For the two crystals conguration the total reectivity is the product of the
3.4. Ray tracing results 63
reectivity of each crystal. The reectivity is dened as
R = I
inc
/I
out
(3.2)
where I
inc
is the incident intensity, while I
out
is the outgoing intensity.
For additional informations on the spectrometer, one should refer to sec-
tion 2.2.
Figure 3.6: Schematic representation of the optical system used for x-ray
ray tracing to simulate the double analyser spectrometer.
3.4 Ray tracing results
In this section the ray tracing results are presented. Several simulations
were performed, for several sets of planes in Bragg reection and for dierent
values of the scattering angle, always in quasi-backscattering geomtery (in
the range 0.5
1.5
o backscattering).
In table 3.1 the settings used for the ray tracing are reported. These
quantities are important because of their contribution to the total energy
64 3. Ray tracing
Table 3.1: Ray tracing settings.
Gaussian source size: 110 40 m
2
(H x V)
Cubes dimension: 0.067 cm
Bragg angle
B
: 88.5
89.5
width as explained in Chapter 1 and in Chapter 2. In particular the source

size contribution to the energy resolution is given by the equation:
E
E
=
_
s
D
_
cot
B
(3.3)
where s is the source size, and D is the optical path after the sample, and
one has for the single pass D = R and for the double pass D = 2R, where R
is the diameter of the Rowland circle.
3.4.1 Resolution functions: DP spectrometer vs SP
one
Resolution functions obtained by Shadow were saved in external data les.
On these data les the compensation procedure for a 55 m pixel size was ap-
plied, in order to make the ray tracing data comparable with the experimental
data (in fact the same compensation macro was applied to all the experimen-
tal data as explained in section 2.4.2). This procedure takes advantage of
the angle-energy relation for Bragg scattering to improve the instrumental
resolution. In gure 3.7 the resolution functions obtained by ray tracing for
the double analyser spectrometer are shown. For all of these data the Bragg
angle was 88.5
. These ray tracing data were obtained for three dierent sets
of planes.
Figure 3.7: In this gure the resolution functions concerning the double
analyser spectrometer for three dierent sets of planes, obtained by Shadow
ray tracing are shown. The Bragg angle for all cases is 88.5
(that corresponds
to 1.5
angle of incidence, i.e. the angle between the incident direction and
normal to the surface). For each set of planes dierent values of FWHM
were found, see table 3.2.
66 3. Ray tracing
Table 3.2: Ray tracing results for the full width at half maximum (FWHM).
On the rst column the set of planes used, in the second the FWHM for the
SP conguration, in the third one the FWHM for the DP spectrometer, and
then in the last column the FWHM of the squared resolution function of the
SP conguration. For all of these data the glancing angle was 88.5
.
(hkl) FWHM
tr
SP
[meV ] FWHM
tr
DP
[meV ] FWHM(SP
2
)
(444) 36.7 27.6 24.7
(555) 16.6 10.8 11.1
(777) 7.3 6.3 5.2
As already pointed out, the double analyser spectrometer is obtained
mounting in the last part of the spectrometer two identical consecutive spher-
ical analyser instead of only one. For this reason the instrumental resolution
function for the double pass conguration was expected to be the product
of the SP resolution function for itself. In order to check this prediction the
comparison between the ray tracing data for the DP spectrometer and the
squared SP instrumental function was performed. In table 3.2 the energy
widths of the ray tracing results presented in gure 3.7 are reported. In the
same table the widths of the squared SP instrumental function are reported
as well.
This comparison is also reported in gure 3.8. It is clear that the two
functions in the central region have exactly the same behaviour. Only 70
meV away from the central peak little dierences arise. Anyway in a good
approximation the behaviour of the double pass resolution function is equal
to the behaviour of the single pass one squared.
In table 3.3 the source size and pixel size contributions (see equation 3.3
Figure 3.8: Comparison between the double pass spectrometer resolution
function and the squared single pass one. The Bragg angle for the ray tracing
data is 88.5
. The values of the FWHM are reported in table 3.2.

68 3. Ray tracing
and equation 2.4) to the energy width, for three dierent reections, are
reported. The reduction of these contributions in the double pass case for all
reections is clear.
Table 3.3: Source size and pixel size energy width contributions. For all of
these data the Bragg angle was 88.5
.
(hkl) Cong E
source
[meV ] E
pixel
[meV ]
(444) SP 8.3 5.7
(444) DP 4.1 2.8
(555) SP 10.4 7.1
(555) DP 5.2 3.6
(777) SP 14.5 10.0
(777) DP 7.3 5.0
An important point for the ray tracing study was the comparison between
the single and double analyser spectrometers, in order to evaluate the real
gain in resolution and contrast. In gure 3.9 the ray tracing results concerning
the Si(555) reection are presented. The Bragg angle was 88.5
. As it is
shown in gure 3.9 the gain in resolution is evident in the DP in comparison
to the SP conguration. The values of FWHM for all of the used set of
planes are reported in table 3.2 . The reduction of the tails of the resolution
function in the DP is very strong. As a matter of fact the contrast in the
DP is 6 10
3
times higher than in the SP for the Si(555) set of planes while
for the Si(444) family it is 4 10
2
times higher in the DP spectrometer than
in the SP one. This is the most important advantage of the double analyser
spectrometer.
Another important aspect studied by ray tracing was the intensity loss
Figure 3.9: Ray tracing results for the single pass spectrometer and double
pass one, for the Si(555) reection. The data are normalized and the Bragg
angle used was 88.5
(i.e. 1.5
angle of incidence). The contrast is about 10

3
for the SP and 6 10
5
for the DP.
for the double analyser spectrometer with respect to the single one. The
reectivity is dened in section 3.3.3.
The dynamical theory predicts total reection, with reectivity R

= 1,
from crystals in Bragg reection with negligible photo-absorption. Total
reection occurs within some region of photon energies (E
c
E/2
E
c
+ E/2) at a given Bragg angle of incidence
c
, and within some re-
gion of glancing angles of incidence (
c
/2
c
+ /2) at a given
energy E
c
. Out of these regions the reectivity goes quickly to zero [2]. So
the main contribution to the total reectivity comes from the rays inside a
70 3. Ray tracing
Table 3.4: Ray tracing results of the intensity loss of the DP spectrometer
with respect the SP one, for each used set of planes in the ray-tracing session.
For all of these data the Bragg angle was 88.5
.
(hkl) I
SP
/I
DP
(444) 1.8
(555) 2.0
(777) 2.9
tight region of energies and angles of incidence. In particular we were inter-
ested in the loss of intensity when using the DP spectrometer instead of the
SP one. In table 3.4 the ratios between the intensity of the single and dou-
ble pass spectrometer, obtained by ray tracing are reported. These results
were obtained with the same angle for three dierent sets of planes.
I
SP
I
DP
represents the intensity loss factor when switching from the SP spectrome-
ter operation to the DP one. So from these data it emerges that using the
Si(444) set of planes for Bragg reection a factor 1.8 of intensity is lost in
the DP spectrometer with respect the SP one.
The last eect studied by ray tracing concerned the geometrical proper-
ties of the image obtained on the detector by the two congurations of the
spectrometer. In particular the main eect was the reduction of this image
on the dispersive direction, due to the reduced angular acceptance when the
double analyser spectrometer is used. This eect is shown in gure 3.10.
As predicted by the dynamical theory, the angular widths of Bragg re-
ections for glancing angles of incidence o /2 (i.e. o backscattering) scale
with tan, where the proportionality constant is E/E
c
[2]:
=
E
E
c
tan
c
(3.4)
Here in exact backscattering geometry
E
E
c
is the angular acceptance of
the crystal. These quantities are well dened for each reection and the
relative values are available in the literature [14].
For the Si(555) = 59.6 rad, for a glancing angle = 1.5
26.2
mrad. This means that only the rays inside this angular region will be
reected by the analyser cubes. This eect has been observed in the ray
tracing study.
The geometrical properties of the image, obtained by the double analyser
spectrometer, were compared with those obtained by the single pass. These
results were conrmed during the experimental session, as it will be shown in
the next chapter. The double analyser spectrometer showed a reduction of
the image in comparison to the single pass one in the dispersive direction. A
reduction of about 35% (shown in gure 3.10) in the image size is observed
along the dispersive direction. It means that the image observed in the DP
case has a size, along the dispersive direction, that is only the 65% of the
image size of the SP case (z
DP
/z
SP
0.65, where z is the size of the
image along the dispersive direction and the pedices DP and SP refer to the
two congurations of the spectrometer). In fact using equation 3.4, for the
FWHM of the Si(555) reection obtained by ray tracing, one obtains that
this reduction is of 35%, that corresponds to a z
DP
/z
SP
0.65, in perfect
agreement with the values obtained by ray tracing.
The same eect was observed during the experimental session, in the
image revealed by the detector.
72 3. Ray tracing
(a)
(b)
Figure 3.10: In gure 3.10a and 3.10b the reduction eect of the image size
along the dispersive direction is shown, as observed by ray tracing. These
images were obtained for the Si(555) family of planes.
Chapter 4
Two spectrometers in
comparison
In this chapter, the comparison between the single pass spectrometer and
the double one is presented. The chapter starts studying the corresponding
resolution curves and it ends presenting data collected by these two dierent
congurations of the spectrometer. The rst part of the work was carried
out using the Si(444) reection, that corresponds to a backscattering energy
of 7908 eV . At the beginning a 88.5
scattering Bragg angle was used, that

is 1.5
o the normal to the analyser. In this way, the reected energy

was a bit dierent, the observed value was 7911 eV . At the end another
conguration was tested, using the reection Si(555), and varying the Bragg
angle, reaching 1.2
o normal.
4.1 Resolution curves
In the double analyser spectrometer the expected resolution curve is the
convolution of the two coupled analysers instrumental function with the
74 4. Two spectrometers in comparison
monochromator one, see section 1.3.
Using the collected data concerning the resolution function, and knowing
the contribution of the post-monochromator, by convolution it was possible to
obtain the instrumental function of the single and double pass spectrometers.
4.1.1 Instrumental function using the Si(444) set of
planes
In table 4.1 it is possible to see all the contributions to the full width at half
maximum for the single and double pass congurations, in the case of the
Si(444) family of planes for Bragg reection.
Table 4.1: Expected width contributions to the instrumental resolution func-
tion, for the Si(444) set of planes
Contribution FWHM
SP
[meV ] FWHM
DP
[meV ]
Source size 8.3 4.1
Pixel size 5.8 2.8
Width post-mono 39.3 39.3
Width analysers 39.3 26.2
Total 56.5 46.7
The pixel size contribution is given by equation 4.1:
E
E
=
_
s
R
_
cot (
B
) (4.1)
where s is the vertical dimension of the source (around 40 m), and R is
the optical path length, that is 1 m for the SP and 2 m for the DP.
4.1. Resolution curves 75
The Pixel size contribution is given by the equation 2.3. Carrying out the
calculations it is easy to see that, for geometrical reasons, the values of the
source and of the pixel contributions in the double pass case are half than
those in the case of the single pass conguration.
The analysers contribution to the FWHM in the case of the DP spectrom-
eter is roughly given by the square of the analyser contribution in the case of
the SP spectrometer. For this latter case, the behaviour of the instrumental
function is quite similar to a Lorentzian, in particular near the elastic peak.
The best expected improvement in the double analyser spectrometer is
not in the FWHM but in the contrast.
A clear estimation of the instrument resolution was obtained by perform-
ing an elastic scattering scan. To reach this goal a little piece of plastic sticky
tape was used. Its fundamental characteristic is that it does not contribute,
in a rst approximation, to the total width (FWHM) of the system. We put
the sticky tape in a vacuum chamber. After the alignment and the focusing
operation, we started to collect the data: rst for the single pass spectrometer
and then for the double one.
In the gure 4.1 the data concerning the single pass conguration of the
spectrometer are plotted.
These data were collected for a Bragg angle of 88.5
, using the a4scan

macro, i.e. varying the incident energy, taking 100 dierent energy values,
and acquiring 5 seconds for every energy point. This image is in semi log-
arithmic scale for the intensity. The data are centered at zero exchanged
energy. For the single pass conguration we observed a FWHM value of
about 53.8 meV , quite close to the estimated value of about 56.5 meV . A
t with a Lorentzian function both in the single and double pass case was
executed to obtain a good estimation of the FWHM.
Figure 4.1: Single analyser spectrometer resolution curve in semi loga-
rithmic scale. Performing a t with a Lorentzian function a resolution of
53.80.5 meV was obtained for this conguration of the system . The Bragg
angle was 88.5
and the used set of planes was the Si(444) one.

In the double pass conguration (see gure 4.2) an improvement in the
resolution was obtained: from a FWHM for the single pass of about 53.8
meV , to a FWHM for the double pass of about 46.9 meV .
Figure 4.2: Double analyser spectrometer resolution curve in semi-
logarithmic scale. In this conguration, by a Lorentzian t, it was obtained
that the system has a resolution of 46.9 0.3 meV . For all of these data
the Bragg angle was 88.5
and set of planes used for Bragg reection was the

Si(444).
This improvement in resolution has a cost in terms of intensity. More
than a factor of ten in the intensity of the elastic peak was lost (for more
information about the intensity loss see later in this section). These mea-
surements were taken by summing two dierent scans. For every scan we
took 100 dierent energy values, and every scan was acquired for 5 seconds.
The most important achievement of the double pass conguration is the
improvement in the instrumental resolution in the tails of the resolution
curve, as it is possible to see in gure 4.3. For values in energy shift few dozens
of meV far from the elastic peak, the double pass spectrometer becomes more
ecient in cutting the intensity on the tails. This means that the main gain
is in the contrast of the resolution function not in the FWHM.
In the double pass data the tails of the resolution curve go down so fast
that it is possible to see some excitations at about 350 meV. These peaks
are the vibrational excitations of the sticky tape, that contains C-H chains.
At 372 meV we can see the C-H stretching, consistently with Raman mea-
surements [20]. At about 460meV , additionally a contribution from the O-H
stretching can be observed, though the intensity is very low there [21].
These peaks are evident in the right side of the gure, i.e. for positive
energy transfer values (Stokes), while they are really weak on the left side
(anti Stokes). In order to explain this dierence it is necessary to consider
that there are three possible processes:
1. Elastic scattering - there is no exchanged energy. The energy transfer
is zero, this corresponds to the central peak in the spectrum
2. Inelastic Stokes scattering - the system absorbs energy and the x-ray
beam looses it. This kind of process is observed for positive energy
transfers, i.e. the peaks on the right side of the spectrum.
3. Inelastic anti-Stokes scattering - the system looses energy and the
emerging photon has an higher energy than the incident one. This kind
of process is observed for negative energy transfers, i.e. it corresponds
to the peaks on the left side of a spectrum.
In terms of observed intensity the anti-Stokes process is disadvantageous,
because it corresponds to a less populated excited state [3]. For this reason
the peaks for negative energy transfer are weaker, simply because the states
corresponding to them are less probable.
At this point comparing the two resolutions in one plot is interesting, see
gure 4.3. From this plot it is evident that, in the high energy tails, the value
of the double pass curve is almost two orders of magnitude lower than for
the rst pass case.
Furthermore it is possible to estimate roughly the contrast dening it as
C = I(0)/I(20), i.e. the ratio between the intensity in the elastic peak and
the intensity at 20 from the elastic peak. In this way we get a contrast for the
single pass C
SP
1200, while for the double pass C
DP
10
5
. This big gain
in contrast is the fundamental advantage of the double pass spectrometer.
It means that the system is working like expected, and that the tails of the
resolution curve are reduced by the second pass, as expected from ray tracing
in section 3.4.
We can as well underline the fact that the level of the double pass tails
is probably still only limited by noise.
4.1.2 Instrumental function using the Si(555) set of
planes
Another measurement of the instrumental function was carried out using
the Si(555) reection with a 135
scattering angle. The data regarding this

measurement are reported in gure 4.4. They were collected using the a4scan
macro, with a counting time of 5s. In table 4.2 all the contributions to the
Figure 4.3: Comparison in semi logarithmic scale between the resolution
functions of the two spectrometer congurations. These measurements were
collected using the Si(444) set of planes for Bragg reection. The data and
the errors are normalized to the maximum in order to compare the double
and the single pass. The contrast is approximatively for the SP C
SP
10
3
and for the DP C
DP
10
5
. The SP resolution function decreases roughly
like 1/E
2
, while the DP one 1/E
3
. The Bragg angle was 88.5
.
Table 4.2: Width contributions to the instrumental resolution function, for
the Si(555) set of planes
Contribution FWHM
SP
[meV ] FWHM
DP
[meV ]
Source size 10.3 5.1
Pixel size 7.1 3.5
Width post-mono 15.4 15.4
Width analysers 15.4 10.3
Total 25.1 19.5
full width at half maximum for the Si(555) set of planes are reported.
The gain in contrast in this case (Si(555)) appears to be negligible (1.510
3
in SP vs 2.2 10
3
in DP), but observing with more attention gure 4.4 and
comparing it with gure 4.3, it is clear that the intensity on the tails of
the DP measurements with the Si(555) reection is at the same level of the
background. The contrast for these Si(555) reection measurements then
cannot be obtained.
In table 4.3 the main characteristics of the spectrometer are reported for
the two used reections.
The big intensity loss without any interesting gain in contrast has made
the Si(555) conguration less interesting at the moment.
4.1.3 Intensity loss
A drawback of the double analyser spectrometer was the quite high intensity
loss with respect to the single analyser spectrometer. Considering every cause
of loss, it was possible to understand the entire intensity loss in the double
analyser spectrometer case compared to the single one (see table 4.4).
Figure 4.4: Comparison in semi-logarithmic scale between the resolution
functions of the two spectrometer congurations, using the Si(555) reection.
The data were collected using the a4scan macro with a counting time of 5s
for both single and double pass congurations. The data are presented as
measured, to show the intensity loss in the double analyser spectrometer (a
factor 37 is lost). The FWHM for the double pass is 22.5 meV vs 24.7 meV
for the single pass.
Table 4.3: Main characteristics of the double pass and single pass spec-
trometers, for the dierent reections used (Si(444) and Si(555)). In the
second and third columns the FWHM for the single and double pass, respec-
tively, are reported. The fourth column reports the intensity loss as the ratio
of the single pass intensity over the double pass intensity. In the last two
columns the contrast for single and double pass congurations are reported.
The contrast was dened as C =
I(0)
I(20)
. The contrast for the Si(555) reec-
tion measurements has not been reported here because, as explained in the
text.
Reection FWHM
SP
FWHM
DP
I
SP
I
DP
C
SP
C
DP
Si(444) 53.8 meV 46.9 meV 23 1.2 10
3
10
5
Si(555) 24.7 meV 22.5 meV 37
Table 4.4: Contributions to the intensity loss in the double pass spectrometer
with respect to the single one. These values were calculated for an incident
energy of 7.9 keV , that is the energy used for the Si(444) reection.
Source Theoretical loss [%]
Air Absorption (40 cm) 38
Analyser grooves 30
Kapton interfaces and grids 15
Reectivity contribution 9
Total loss DP with respect to SP 92
In order to measure the intensity loss, the instrumental function of the
single analyser spectrometer and the double one were collected in the same
experimental conditions. They were relevant to get the real intensity loss.
The results are shown in gure 4.5.
Figure 4.5: Resolutions comparison in logarithmic scale for the two spec-
trometer congurations. These data were collected by the a4scan macro with
a counting time of 2s for both the single and the double pass conguration.
The data are presented as measured, to show the intensity loss in the double
analyser spectrometer.
Thanks to these measurements it was possible to understand that a factor
23 (for the Si(555) it is about a factor 37) in the intensity was lost using the
double analyser spectrometer. This means that only about 4% of the single
4.2. Data from samples 85
analyser spectrometer intensity reached the detector in the double analyser
conguration, as compared to the 8% loss expected from the estimations
reported in table 4.4. The missing 4% intensity loss contribution is probably
due to the cubes misalignment between the rst and the second analyser.
Because of lack of beam-time, it was not possible to perform further tests to
conrm the reason of this intensity loss.
4.2 Data from samples
After the comparison of the resolution curves, the double analyser spectrome-
ter was tested, analysing its performances in some measurements on samples.
An important step was the choice of suitable samples. As a matter of
fact it was necessary to look for excitations compatible with the resolution
of the instrument. As it is shown on the last section (paragraph 4.1) the
FWHM of the instrument is of the order of some tens of meV both in the
single analyser spectrometer and in the double analyser one. Two interesting
excitations compatible with the values of FWHM are:
the molecular vibrational excitations in liquid water, that are few hun-
dreds of meV distant from the elastic peak.
the d-d electronic excitations, few eV distant from the elastic peak.
In the following sections the data regarding these samples will be pre-
sented.
4.3 Liquid water vibrational excitations
4.3.1 Theoretical background
The nuclei in a molecule are in a continuous state of vibration [22]. An
important feature of this dynamics is that they can be described by a limited
number of basic vibrations, known as the normal modes. A normal mode is a
vibration in which all the nuclei oscillate with the same phase and frequency.
The water molecule has three normal modes and every possible vibration of
the molecule can be described as a superposition of these three modes.
The normal modes of water are presented in gure 4.6. Because the mo-
tion of the nuclei, in the
1
and
3
vibrations, is nearly along the direction
of the O-H bonds, these modes are often referred to as O-H stretching vibra-
tions. Also, because the H nuclei in
2
move in almost perpendicular direction
to the bonds,
2
is referred to as the H-O-H bending vibration. In fact,
1
involves a small amount of H-O-H bending, and
2
involves a small amount
of O-H stretching. The mode
3
is called asymmetric stretching vibration to
distinguish it from the symmetric component of the stretching
1
.
In addition to the three normal modes there is also another type of rel-
evant molecular vibrational excitations, the librations. A libration is a type
of reciprocating motion in which an object with a nearly xed orientation
repeatedly rotates slightly back and forth. In gure 4.6 also the three libra-
tions around the x,y and z axis are presented. The librations are measurable
in the infra-red absorption spectrum [23], so the peaks visible by infra-red
and raman spectroscopy are often combinations of the normal modes and
librations.
The transition of a water molecule from its vibrational ground state to
the excited state described by the
2
mode is associated with the absorption
4.3. Liquid water vibrational excitations 87
band centered at 197.95 meV , see table 4.5 [24]. During this transition, the
quantum number
2
characterizing the
2
mode changes from 0 to 1, while
the quantum numbers
1
and
3
, characterizing the
1
and
3
modes remain
equal to zero. Similarly, the transition from the ground state to the state in
which only the rst normal mode is excited (symmetric stretching) - the state
with quantum numbers
1
= 1,
2
= 0 and
3
= 0 - is associated with the
absorption band centered at 453.39 meV . For the state (
1
,
2
,
3
)=(0,0,1), i.e.
purely asymmetric stretching, the absorption band is centered at 466.20 meV .
The measurements of the normal modes of water give important information
about the properties of the H
2
O molecule. For example the OH stretch
frequency has proven to be a very sensitive measure of the strength of the
hydrogen bond [25].
Figure 4.6: Shown schematically, the main vibrations occurring in water.
On the top the normal modes, on the bottom the librations.
Table 4.5 lists the energies of some calculated [24] and measured vibra-
tional absorption bands of water in the vapour state [26] [27] [28] [29].
For a hydrogen bonded water molecule, usually a red shift is measured.
Table 4.5: Theoretical and experimental values of the water normal modes
in the vapour state.
(
1

2

3
) Theoretical Energy [meV ] [24] Experimental Energy [meV ][26] [27]
(0 0 1) 467.02 466.20
(0 1 0) 197.55 197.95
(1 0 0) 454.06 453.93
(2 0 0) 893.79 893.89
(0 0 2) 924.70 924.12
It originates from the deeper potential well in the vibrationally excited state.
The origin of such behaviour is traced back to the elongation of the O H
distance in the molecule and the shortening of the O H hydrogen bond
distance. This leads to an increase of the attractive forces caused by the elec-
trostatic, the induction and the dispersion forces. Also in the O-H stretching
measurements it is always visible a negative energy shift due to the coupling
between the vibrations of dierent molecules. For this reason in some exper-
iments the HDO is used in place of the H
2
O. For more information about
these shifts see [25] section 3.2 and [22] pages 229 - 242. It is easy to under-
stand that the stretching bands in pure H
2
O are quite dicult to interpret.
This interpretation is still a matter of discussion. In general it is possible to
distinguish three principal diculty sources about the interpretation of the
liquid water vibrational spectrum [25]:
1. The frequencies of the two O-H stretching vibrations,
1
and
3
, and
that of the rst overtone of the bending vibration, 2
2
, are close to each
other.
2. Each of these vibrations may couple with the vibrations of neighbouring
molecules, causing a splitting of each band. Since the band frequencies
are closely spaced, the split bands overlap.
3. The overlapping
1
and 2
2
modes, in Raman and infra-red spectrum,
may be in Fermi resonance with each other (that is, 2
2
may borrow
intensity from
1
) shifting and modifying the shape of the peak. Fur-
thermore, owing to perturbations of neighbouring molecules, the two
O-H bonds of a given molecule may not be identical; consequently the
3
vibration may not be strictly asymmetric, so that it may also par-
ticipate in Fermi resonance with 2
2
.
Mainly these are the reasons of variation in the peak position regarding
the O-H stretching as for the theoretical values. In literature many studies
of the O-H vibrational spectrum are available. For example Walrafen et al.
[26] or Ricci et al. [30] studied the vibrational spectra of water around the
stretching region varying the temperature of the sample. They ascribed the
structure in the Raman stretching band to the presence of water molecules
forming dierent hydrogen bond environments. They observed that on in-
creasing the temperature the peak position moves toward higher energy val-
ues, i.e. near the theoretical single molecule value. Segre interpreted the
experimental results as a breakdown of intermolecular structure at higher
temperatures [26].
In gure 4.7 it is possible to see the liquid, solid and gaseous water vibra-
tional infra-red spectra [25] for the O-H stretching.
Figure 4.7: Infra-red spectroscopy of H
2
O around the O H stretching
energies, for three dierent states: vapour at 25
C, liquid at 25
C and ice at
83
C [25]. The energy shift due to the temperature change is clearly visible.
4.3.2 Experimental results: SP spectrometer vs DP
one
During the experiment, data regarding the liquid water vibrational excita-
tions were collected, for two values of the scattering angle (corresponding to
a reection and transmission geometry respectively).
The Si(444) and the Si(555) reections for the energy selection, in quasi-
backscattering conguration, were used (
Bragg
= 88.5
).
The sample used for this part of the experiment was puried water con-
tained inside an aluminium support with two kapton windows along the beam
path.
The usual data collection procedure started with the calibration of the
overall tracking in the energy interval of interest. Three energy reference
points (0.5 eV , 0.0 eV and 1.5 eV ) were dened. After that the a4scan
macro was utilized (see section 2.4).
In the single pass conguration the intensity of the signal was strong, so
it was possible to use a short collection time. As a matter of fact, for these
measurements we used the a4scan macro, scanning 150 points between 0.5
eV to +1 eV , counting 5 s for every energy point.
On the other hand, in the double pass spectrometer conguration a big
loss of intensity was observed. Using this set-up it was necessary to spend
much more time than in the previous one. Indeed, in order to obtain good
results, ten a4scan were summed. Every scan was made of 150 points, using
a collection time of 20 s compared to 5 s for the single pass case.
The data regarding these measurements are shown in gure 4.8 for both
the single and the double pass conguration.
From gure 4.8 it is easy to understand that the contrast of the single
analyser spectrometer is not enough to show the vibrational excitation peaks,
except for the OH stretching peak which is possible to see around 450meV
energy transfer. In the double analyser set-up, instead, it is possible to see
also the O-H bending (around 200 meV ) and the stretching overtone (around
870 meV ) as well.
Figure 4.8: Comparison between molecular vibrational excitations of water
data collected in single and double pass, for a momentum transfer of q =
7.3

A
1
. The double pass data are scaled to have the same elastic intensity
as the single pass ones. The abscissa represents the energy transfer, or the
energy distance from the elastic peak. The elastic peak is at 7909.9eV and
the reection used for the energy selection is Si(444).
To determine the water vibrational excitations energies it was useful to
perform a t with a Pearson function centered at the elastic peak and to
subtract from the experimental data the t. In this way it was possible to
see and analyse directly only the excitation bands and, in the end, to compare
these data with those from other experiments. The result of this procedure
is shown in gure 4.9.
Figure 4.9: In this gure it is possible to observe the original data with the
t to the elastic peak and the data after subtraction of the elastic line around
the O-H stretching excitation energy.
An additional measurement of the water vibrational spectrum using the
Si(555) reection was performed, as shown in gure 4.10. These data were
collected using a scattering angle of 135
, that corresponds to an exchanged

momentum of 9.3

A
1
. The plot was obtained by summing six dierent
a4scan macro measurements, each of which is composed of 150 points ob-
tained by using a collection time of 20 seconds. Looking at the plot reported
in gure 4.10 it is clear that the loss of intensity is very strong, using this
reection. As a matter of fact, the intensity loss of the water measurements
is about a factor 50 with reference to the elastic peak. For this reason these
data are really more noisy than those collected using the Si(444).
The position of the O-H stretching peak is at an energy transfer of 448
meV , for the Si(555) measurement at 9.3

A
1
. In addition, the Si(444)
(with a exchanged momentum of 7.3

A
1
) measurements gave for the O-H
stretching peak position a value of 451 meV , that is 16 meV lower than
the measurements performed for an exchanged momentum of 3

A
1
. This
dierence is due to the dierent exchanged momentum and possibly also to
a dierent composition of the visible peaks.
All together, measurements of the stretching peak position for three dif-
ferent values of momentum transfer were performed in order to conrm the
dispersion in exchanged momentum. In table 4.6, the results concerning these
three measurements are presented, while in gure 4.11a the same data are
plotted. From these measurements it is easy to understand that the position
of the stretching excitation is strongly inuenced by momentum transfer. To
pinpoint this result a detailed analysis for more values of exchanged momen-
tum is needed, and it could be the topic of future measurements.
4.3.3 Comparison to other techniques
One of the most important steps of this work is to compare the double anal-
yser spectrometer results and the data obtained from other experiments, in
Figure 4.10: Plot of the water spectrum measured using the double analyser
spectrometer, using the Si(555) reection. The exchanged momentum is q =
9.3

A
1
that corresponds to a scattering angle of 135
. The OH stretching
peak was observed at 448 meV .
Table 4.6: Stretching peak dispersion
Q Exchanged momentum (
A
1
) Stretching Energy (meV )
3.0 467
7.3 451
9.3 448
2 3 4 5 6 7 8 9 10
440
445
450
455
460
465
470
475
Q Exchanged momentum [
1
]
S
t
r
e
t
c
h
i
n
g

p
e
a
k

p
o
s
i
t
i
o
n

[
m
e
V
]

Dispersion of the stretching peak position
(a)
380 400 420 440 460 480 500 520 540 560 580 600
10
1
10
0
Energy transfer [meV]
I
n
t
e
n
s
i
t
y

[
a
.
u
.
]

Q=7.3
1
Q=3.0
1
(b)
Figure 4.11: In gure 4.11a the plot of the stretching excitation peak posi-
tion vs momentum transfer is presented. A clear evidence for the momentum
transfer dispersion is shown in this plot. In gure 4.11b the vibrational spec-
trum of liquid water near the OH stretching peak for two dierent exchanged
momentum values is reported. These two measurements were performed us-
ing the Si(444) reection.
order to verify the quality of our measurements and fully understand the
measurements collected during the experiment.
The molecular vibrational excitations measurements of water obtained
during these tests were not the rst observation of molecular vibrational
excitations of water by inelastic X-ray scattering. As a matter of fact in
October 2000 the ID16 team demonstrated that it is possible to observe
water molecular vibrational excitation by IXS with a single pass spectrometer
[31]. The data corresponding to those measurements compared to the double
analyser spectrometer results are shown in gure 4.12. The accumulation
time required for these spectra, collected by ID16 team, was about 40 hours.
In gure 4.12 it is possible to see the spectra as measured without any kind of
smoothing or binning. In the old measurements the momentum transfer was
2.9

A
1
. Otherwise, the new measurements were collected for three dierent
values of momentum transfer: 3

A
1
, 7.3

A
1
and 9

A
1
.
In the end, the data obtained by the double analyser spectrometer set
up were compared to data collected by Raman light scattering and Inelastic
Neutron Scattering (INS) techniques. This kind of comparison is really im-
portant to understand the nature of the observed peak in the scattered x-ray
intensity.
To achieve this goal, data from various papers available in the litera-
ture were used, [30] [32] [26]. In gure 4.13 the data collected by dierent
techniques are shown [30] [32] [26]. It is possible to distinguish the bending
around 220 meV , the stretching around 450 meV and the stretching over-
tone around 850 900 meV , very close to the theoretical values, see section
4.3.1. For example considering the O-H stretching, it is possible to see that in
Raman light scattering the peak of the O-H excitation was seen in the range
404 440 meV , while by INS it was observed in the 430 443 meV range,
0.2 0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
10
2
10
1
10
0
10
1
10
2
10
3
10
4
Energy transfer [meV]
I
n
t
e
n
s
i
t
y

[
a
.
u
.
]

Double analyser spectrometer water vibrational excitations
First evidence of water vibrational excitations by IXS (C. Halcoussis et al. 2000)
Figure 4.12: Comparison with data collected by the ID16 team, October
2000 [31]. The measurements collected by the double analyser spectrometer
reveal the O-H stretching excitation at 451 meV much more clearly.
and our data show this peak at 451 meV at 7.3

A
1
. The peak observed
around 400 meV (by Raman light scattering) is the combination of libration,
stretching excitations (
1
) and the bending overtone 2
2
. The asymmetric
stretching mode is not expected to contribute to the isotropic Raman in-
tensity, due to symmetry selection rules [30]. Furthermore this peak is also
aected by the shift due to the Fermi resonance and, as explained in section
4.3.1, the coupling between several molecules vibrations. Regarding the peak
corresponding to the stretching modes probed by INS, these data represent
the simultaneous eects of stretching and libration (in the three dimensions)
of the O-H bond.
Table 4.7: Rough values of the stretching and bending excitations measured
using dierent techniques, including the double analyser IXS spectrometer.
The data regarding INS and Raman light scattering are available from the
literature, [30] [33] [32].
Excitation Raman [meV] INS [meV] DP IXS[meV]
O H stretching 410 440 451
O H bending 205 210 206
Referring to gure 4.13 it is possible to see that the same excitations
detected by dierent techniques are around similar energy values. Later
in this chapter deconvolution of the stretching peak will be presented to
investigate approximatively the weight of the components inside the peak
revealed by IXS.
Figure 4.13: Comparison of water molecular excitations collected by three
dierent techniques: Raman Light Scattering [30] [33] [34] [26], Inelastic
Neutron scattering [30] [32] and Inelastic X-ray Scattering. Those regarding
INS represent the density of state (DOS). The data were arbitrarily scaled to
be presented on the same scale. In the inset a zoom on the stretching overtone
region is presented. The Raman measurements inside the inset are scaled for
comparison.
Figure 4.14: Gaussian t of the O-H stretching band of water, collected
using the double analyser IXS spectrometer. This t nds a maximum for
the O-H stretching at 451.0 0.7 meV , and a FWHM of 80.8 1.9 meV .
4.3.4 Further considerations
In order to have a better estimation of the OH stretching energy position,
a t of the stretching inelastic peak was performed.
This t was carried out by a Gaussian function and the results are pre-
sented in gure 4.14. The result of this calculation issued the position of the
maximum concerning the stretching peak at 451.0 0.7 meV , and a FWHM
of 80.8 1.9 meV .
This value for the O H stretching excitation, is not only the result of
an average over several excitations, but it is also shifted for the eect of the
interaction between the molecules in the liquid state. To take into account
all these eects further investigations are necessary, in particular scanning
the water vibrational spectrum for several values of the sample temperature,
as made, using the Raman scattering technique, by Larsen et al. [21]. As
a matter of fact studying the system for dierent temperatures gives more
information about the eect of the interaction between dierent molecules.
Anyway the interpretation of the peculiar line-shape of the OH and OD
stretching bands of the Raman spectrum of water is still a matter of discussion
[30].
Furthermore another Gaussian t was performed on the data collected
by the DP spectrometer in the region of the stretching overtone, in order
to identify its position. In gure 4.15 the results of this t are shown. The
overtone by this t was found at 879.0 9.0 meV , while by Raman light
scattering [26] it was found at 836.6 meV .
As observed in the literature [34] [26] for O-H stretching of liquid water
and for its overtone, we observed a red-shift with respect to the theoret-
ical values calculated for the free molecule. It is interesting to note that
the energy position of the overtone is the 3% lower than the double of the
O H stretching, this dierence is probably due to anharmonicity eects
(such as Fermi resonance). In order to better characterize this shift, further
investigations are needed, in particular a study of the excitations varying the
temperature of the sample.
Anyway the purpose of this work was not the study of the vibrational
spectra of water in detail, but the verication of the reliability of the IXS
data collection using the double analyser spectrometer in order to investigate
the water vibrational spectra in the region of the bending and stretching ex-
citations. Comparing other techniques results with the double analyser spec-
trometer IXS ones we nd an overall agreement between the measurements
Figure 4.15: Gaussian t of the data collected by the DP spectrometer in
the region of the O-H stretching overtone. The peak was found at 879.0 9.0
meV .
available in literature and the data collected by the double analyser spec-
trometer. The quality and the contrast of these measurements demonstrate
that IXS with the double analyser spectrometer could be a new powerful tool
to study the vibrational spectra of water, and similar issues.
4.4 Test on NiO powder: d-d excitations
Transition metal oxides show some fascinating electronic properties widely
investigated in last 70 years. For example the simple monoxides MnO, CoO,
NiO and CuO are insulators with gaps of up to several electron volts, but the
large size of the insulating gap cannot be explained adequately in one-particle
band-structure formalism such as the Local Density Approximation (LDA).
The 3d electrons and 3d holes remain localized at the transition metals ions
in several oxides and show not band-like, but quasi-atomic like character [35].
In contrast to free ions, where the d states are degenerate, the d states of the
transition-metal ions in the oxides are energetically split owing to the crys-
tal eld provided by the surrounding oxygen ions. Transitions between 3d
states are of great inuence on the optical properties of the transition metal
oxides. These oxides were among the rst solids found where the band pic-
ture fails to describe a wide range of properties. From simple band structure
calculations, the 3d states are expected to form an incompletely lled con-
duction band, leading to metallic conductivity of the oxides similar to that
of the corresponding transition metals, which is not observed. These oxides
belong to the class of Mott-Hubbard or charge-transfer insulators, because a
strong Coulomb correlation prevents the electrons from forming a 3d band
and localizes them at the transition metal ions. So the electrons cannot move
freely and an energy of several electron volts is needed for electron transfer
4.4. Test on NiO powder: d-d excitations 105
between neighbouring transition metal ions[35]. All these properties make
the electronic structure of metal transition oxides very interesting.
In particular the dipole-forbidden d d electronic excitations of NiO are
suitable to test the double analyser spectrometer because they appear at less
then 6 eV [36]. The two lowest lying excited states are
3
T
1g
and
3
T
2g
type
and they are situated at 1 eV and 1.8 eV respectively. In gure 4.16 the total
energy diagrams of the lowest d d excitations in NiO are shown.
Figure 4.16: NiO lowest energy dipole-forbidden d-d excitations, observed
at 1 eV and 1.8 eV [36].
For the study of electronic excitations IXS is easy to understand in terms
of the dielectric function[4]. As a matter of fact the double dierential cross
section is readily understood in terms of the longitudinal dielectric function.
The probability of scattering into a solid angle element [, + d] and an
energy-transfer range [, + d] (with = 1) is [37]:
d
2
dd
= (
d
d
)
Th
S(q, ) (4.2)
where (d/d)
Th
is the Thomson scattering cross section (specic for x-
ray scattering from electrons), and S(q, ) is the dynamic structure factor,
which is related to the dielectric function
L
(q, ),
S(q, ) =
q
2
4
2
e
2
Im[
L
(q, )]
1
. (4.3)
When large momentum transfers are of interest IXS is typically used. In
fact in the literature it is possible to nd several publications where IXS
at synchrotron radiation sources is used [36] [37] [38] [39]. The relevant
excitation range which is possible to study using this method is well suited
for studies of well localized valence-electron excitations.
4.4.1 NiO measurements
The sample used was a NiO powder inside a kapton support at room-temperature.
The NiO data were collected for a single value of momentum transfer, 7.3
A
1
.
In gure 4.17 the comparison between the single and the double pass
measurements are reported.
These measurements display excitations within the 3d band of the Ni
2+
ion[35]. These excitations also have been studied and characterized in detail
by using not only IXS [37][38] , but also resonant IXS [36] and EELS [35]
In these measurements there is clear evidence of excitations at 1.071.09
eV, 1.85 eV, 3.11 eV, 3.723.79 eV and 4.244.31 eV, in agreement with the
results reported in literature [36] [37] [38] [39].
From these results it is clear that the double analyser spectrometer is
reliable in analysing the d d spectra of NiO as well.
4.4. Test on NiO powder: d-d excitations 107
Figure 4.17: Comparison of NiO SP and DP measurements. These mea-
surements were collected with a momentum transfer Q of 7.3

A
1
and using
the Si(444) reection. Peaks are clearly visible at 1.071.09 eV, 1.85 eV,
3.11 eV, 3.723.79 eV and 4.244.31 eV, in line with the data available in
the literature [37]. The vertical lines indicate the positions of the excitations.
Conclusions
As it is clear from the results shown in the last chapter, the resolution power
of the double analyser spectrometer is quite higher than the one of the single
analyser spectrometer. This result is in line with the outcome of the ray trac-
ing analysis, which gives a reliable estimate of the spectrometers behaviour.
As a matter of fact the ratio between the FWHM of the instrumental func-
tion for the single pass and the double pass spectrometers, was the same in
the ray tracing analysis and in the experimental measurements. For exam-
ple considering measurements and ray tracing analysis corresponding to the
Si(4, 4, 4) reections, we had
FWHM(SP)
FWHM(DP)
1.3 in both cases.
The most important improvement introduced by the double analyser spec-
trometer is however not in the FWHM, but in the contrast of the instrumental
resolution function. In fact considering this parameter, we obtained that the
contrast of the DP spectrometer is one hundred times higher than the one
of the SP, in accordance with the prediction obtained by ray tracing. The
measurements presented in gure 4.3 show clearly the improvement in the
instrumental resolution function.
The measurements performed on the two chosen samples conrm the
higher performances of the double analyser spectrometer. For example gure
4.8 shows that the molecular vibrational excitations of liquid water are very
dicult to reveal using the single analyser spectrometer (the excitations in-
110
tensity is roughly at the same level as the background), while they are well
resolved by the double pass spectrometer.
Both NiO d d excitations measurements and liquid water vibrational
spectra ones, are in good agreement with data available in the literature.
The comparison between the data I collected and the ones available in
the literature concerning the liquid water vibrational spectra (presented in
gure 4.13), underlines the reliability of the double pass spectrometer. These
data complement those already obtained with light and neutron scattering,
and give us the possibility to study these excitations with more detail than
possible today.
In conclusion the double pass spectrometer can be considered as a new
tool to broaden the physical processes observable by inelastic x-ray scattering.
Acknowledgements
Il ringraziamento pi` u grande è quello nei confronti dei miei genitori e della
mia famiglia, senza di loro tutto questo non sarebbe stato possibile.
Devo ringraziare Giulio Monaco per tutte le cose che mi ha insegnato
durante la stesura di questo lavoro, ho imparato di pi` u nella preparazione
di questa tesi che nellarontare esami alluniversità. Insieme a lui devo
ringraziare anche il prof. Ruocco che mi ha dato la possibilità di partecipare
a questo progetto.
Grazie a Ele, senza la quale sarei solo un paio di ruvide chele.
Un grazie speciale va a Giacomo per tutto laiuto e lamicizia che mi ha
mostrato e per la disponibilità che lo ha sempre contraddistinto.
Grazie a Leonetto per tutte le avventure, le follie, le cavolate e i consigli,
le genialate e le demenze, e per avermi dimostrato che un vero amico cè
sempre e non solo a parole.
Grazie ad Alessio, per la sua amicizia ed il suo aiuto (inoltre senza di te
la formattazione di questo documento sarebbe stata impossibile) e grazie a
nche a Luca, senza i tuoi consigli mi sarei perso la metà delle scadenze..
Grazie a Bea e a Laura, per come mi hanno accolto. A Simo, Tuomas,
Valentina e Roberto, è stato bellissimo lavorare con voi.
Grazie ai ragazzi di Alsace Lorraine, Giuseppe, Davide, Miguel, Rita, Ivan
e Pilar, mi avete fatto sentire a casa. Grazie al Peverini e a Dionisio per le
112
nottate con la chitarra e il violino, innaate di vino e risate.
Grazie al dottor Lucchetti, per la sua gentilezza e perche è bravissimo a
fare il suo lavoro.
Un grazie sincero di cuore a tutti voi.
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Index
Analyser, 14, 24, 47, 71
Beamline, 29
Bragg diraction, 16
Compensation, 45, 47, 64
Contrast, 25, 62, 75, 103
experimental, 79, 83, 91
ray tracing, 68
d-d excitations, 105
Double analyser spectrometer
see Double pass spectrometer, 25
Double dierential cross section, 2, 6,
106
Double pass spectrometer, 24, 25, 36,
67, 73, 91
optical system, 62
Dynamic structure factor, 6, 9, 106
FWHM, 25
experimental, 74, 75
ray tracing, 66, 68
IXS, 1, 2, 9
double dierential cross section, 3
Dynamic structure factor, 6
experimental aspects, 11
non resonant, 4
resonant, 4
spectrometer, 14, 30
Maxipix detector, 44, 45
NiO, 105
measurements, 107
Ray tracing, 53, 57
Resolution function, 59, 64, 74
experimental, 80, 81
ray tracing, 65, 67
SHADOW, 57
Single analyser spectrometer
see Single pass spectrometer, 15
Single pass spectrometer, 15, 30, 32,
67, 73, 91
optical system, 62
Synchrotron, 11
accumulation ring, 13
Index
Undulator, 13
Water vibrational spectra, 86, 91
theoretical background, 86

Santagati Tesi

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Ai miei genitori

, t) gives the probability of nding an electron at time t at r

with respect to the normal),

width as explained in Chapter 1 and in Chapter 2. In particular the source

. The values of the FWHM are reported in table 3.2.

angle of incidence). The contrast is about 10

scattering Bragg angle was used, that

o the normal to the analyser. In this way, the reected energy

, using the a4scan

and the used set of planes was the Si(444) one.

and set of planes used for Bragg reection was the

scattering angle. The data regarding this

, that corresponds to an exchanged

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