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Emission spectra: All objects emit thermal radiation
characterized by a continuous distribution of wavelength
(continuous spectrum).
When a gas at low pressure is subjected to an electric
discharge it emits radiations of discrete wavelengths
(line spectrum).
a
aa a
3
Rydberg constant RH= 1.097 x 107/m
The wavelengths of the other series lines in the
hydrogen spectrum are given by the equation
O
r
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r
r
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r
r
Although no theoretical basis existed for these
equations, they are in agreement with the experimental
results.
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m1] (a) What value of n is associated with the 94.96-nm
spectral line in the Lyman series of Hydrogen ? (b)
Could this wavelength be associated with the Paschen
or Balmer series ?
O &
'(O
Ô Ô
Ô
r
×
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(
r r
r
× ×
The shortest wavelength for this series corresponds to n = for
ionization. For n = , gives Ȝ = 820 nm. This is larger than 94.96
nm, so this wave length cannot be associated with the Paschen
series.
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r r
r
r × ×
with n = for ionization, Ȝ min = 365 nm. Once again the shorter
given wavelength cannot be associated with the Balmer series.
6
3
3
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L=mev r = n
n = 1, 2, 3, . . .
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me = mass of the electron
Y
v = speed of the electron in the
orbit
r = radius of the electron¶s orbit
Electric potential energy of the H-
atom is r r 1
Y
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Ñ
) + ,
& %
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#
Apply Newton¶s 2ND law to the electron, the electric force
exerted on the electron must be equal to the product of mass
and its centripetal acceleration (Ñ2(
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Vonization energy = minimum energy required to ionize
the atom in its ground state
= 13.6 eV for H-atom
From the equation Ei ± Ef = h f
Frequency of the photon emitted during transition of the
atom from state i to state f is
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r
O + # 9
When spectroscopic techniques improved, it was found
that many of the lines in the H-spectrum were not
single lines but closely spaced groups of lines. The
lines appear split when the H-vapour was kept in
magnetic field.
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mÔ apectral lines from the star ȟ-Puppis: aome
mysterious lines in 1896 in the emission spectrum of
the star ȟ-Puppis fit the empirical equation
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.0 '|( The electron in a H-atom makes a transition from the
n=2 energy level to the ground level (n=1). Find the
wavelength and the frequency of the emitted photon.
(B) Vn interstellar space highly excited hydrogen atoms called
Rydberg atoms have been observed. Find the wavelength to
which radio-astronomers must tune to detect signals from
electrons dropping from n=273 level to n=272.
(C) What is the radius of the electron orbit for a Rydberg atom
for which n=273 ?
(D) How fast is the electron moving in a Rydberg atom for
which n=273?
(E) What is the the wavelength of the radiation from the
Rydberg atom in part (B) if treated classically ?
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r r r
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r
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A Ñ*Ñ **- + '(*'<(
r
rY
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.0 According to classical physics, a charge e moving
with an acceleration a radiates at a rate
d 1 e 2a 2
dt Y o c
'( ; ) )) *
) -)-
r
t Y r o
'
( Find the time interval over which the electron will
reach r = 0, starting from ro = 2.00 x 10±10 m
O| ) Ñ
r r
ö
r YV YV
r r r
YV
r
YV
ñ Y
r r r
r r
ö
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r r r r
r
r r r r
rY V
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m A hydrogen atom is in the first excited state (n = 2).
Using the Bohr theory of the atom, calculate
(a) the radius of the orbit
(b) the linear momentum of the electron
(c) the angular momentum of the electron
(d) the kinetic energy of the electron
(e) the potential energy of the system and
(f) the total energy of the system.
m A photon is emitted as a hydrogen atom undergoes a
transition from the n = 6 state to the n = 2 state. Calculate
(a) the energy
(b) the wavelength
(c) the frequency of the emitted photon.
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m 'a) Construct an energy-level diagram for the He+ ion (Z
= 2). (b) What is the ionization energy for He+ ?
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aince U has spherical symmetry, it is easier to solve the
schrodinger equation in spherical polar coordinates (r, ș, ij):
r is the radial coordinate is the radial distance from the origin.
<
-$# r
x 2 y 2 z 2 Y
r
ș
O
Angular coordinate ș specifies the angular position
Y relative to the
z-axis. ș is the angle between z-axis and r
Ô
Vt is possible to separate the variables r, ș, ij and their
corresponding wave functions can be written as
] U J Ô ö] × U J Ô
#
6# 7 ö # *-
Y
r#
@#
r
6# 7 ö
Plot of the probability of finding the electron as a function of
distance from the nucleus for H-atom in the 1s (ground)
state. Probability (P1s(r)) is maximum when r equals to (Bohr
radius). r= ao
2
A
Cross-section of
25
the spherical
electronic charge
distribution of H-
atom in 1s-state.
? ) ;Ñ +- + ,
, ;Ñ +- / 01 / 2
r
# #
r 6# 7 ö r
@ rY
2s is spherically
symmetric (depends only
on r).
2 E2 = E1/4 = ±3.401 eV
(1aT excited state).
a
2
./0 , @,?),: For a H-atom, determine the number
of allowed states corresponding to the principal quantum
number n = 2, and calculate the energies of these states.
)-
When n= 2, can have the values 0 and 1.
Vf =0, m can only be 0.
Vf =1, m can be -1, 0, or +1.
ao, we have a 2s state with quantum numbers 6 6
and three 2p states for which the quantum numbers are
/ ,/
All these states have the same principal
/ 6
quantum number, ×
/ /
× En =(-13.66eV) Z2 /n2
E2 =-(13.66eV)/22=-3.401eV
.0 @,?),! Probabilities for the electron in H-atom:
Calculate the probability that the electron in the ground state
of H-atom will be found outside the Bohr radius.
)-
The probability is found by integrating the radial probability density
for this state, P1s(r), from the Bohr radius a0 to Ú .
r#
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Ô 6# 7
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+ ,
)-
The most probable distance is the value of r that makes the radial
probability P(r) a maximum. The most probable value of r is
obtained by setting dP/dr= 0 and solving for r.
r# r
@#
r
6# 7 ö î Ô
r
ö ö
r
î Ô r
ö ö
r
r
r Ô Ô
r
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r r
r r Ô
r
r
r ö
?+*+
)Ñ)-+ # *-
.!0a3 %)$ 0Ô|)?+
)Ñ)+,)*
r r rr
×
r r×r
where ke is the the Coulomb constant, q1 and q2 are the
charges of the electron and the nucleus, and ȝ is the
r
reduced mass, given by
r
The wavelength for n = 3 to n = 2 Transition of the
hydrogen atom is 656.3 nm (visible red light). What are
the wavelengths for this same transition in (a)
positronium, which consists of an electron and a
positron, and (b) singly ionized helium ?
)-
The reduced mass of positronium is less than hydrogen, so the
photon energy will be less for positronium than for hydrogen. This
means that the wavelength of the emitted photon will be longer
than 656.3 nm.
On the other hand, helium has about the same reduced mass but
more charge than hydrogen, so its transition energy will be larger,
corresponding to a wavelength shorter than 656.3 nm.
All the factors in the given equation are constant for this problem
except for the reduced mass and the nuclear charge. Therefore,
the wavelength corresponding to the energy difference for the
transition can be found simply from the ratio of mass and charge
variables.
+ )Ñ) )+ )
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-
r
ö
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r
r r
r
r r
r
r
r
.!0 a3 %)$ 00Ô For a spherically symmetric
state of a H-atom the schrodinger equation in spherical
coordinates is
r r r r
r
3
r # # # #
ahow that the 1s wave function for an electron in H-
atom
Ô #
Ô 6# 7
Y
Y
]
ö ö ]
Y
ö u
6u 7 uö r
.0
) 4-- -
&
The energy U of the electron with a magnetic moment
Y Y Y Y
C in a magnetic field # is '
C # According to
quantum mechanics, there are discrete directions allowed for
Y
the magnetic moment vector C with respect to magnetic field
Y
vector # Y Y
C ö O
aince r
Y
one finds that the direction of O is quantized. This means
Y
that LZ (the projection of O along the z-axis mdirection
Y
of # ] can have only discrete values. The orbital magnetic
quantum number Gu specifies the allowed values of the z-
B &u
!
Y
O 6 u Ô7
u
a
&2?Ô
22Ô &2/
&2CÔ
$6)?D)7
$)
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2Ô2/ &2/
) 6)CD)7 ) 6)?D)7
a
a
5
5
a
.0 4-- -
The quantum numbers n, ), m) are generated by applying
boundary conditions to solutions of the achrodinger equation.
The ) does not come from the achrodinger
equation. The experimental evidence showed the necessity
of the spin magnetic quantum number which describes
the electron to have some intrinsic angular momentum. This
originates from the relativistic properties of the electron.
There can be only two
directions for the spin angular
Y
momentum vector spin-up and
spin-down as shown in the figure:
apin is an intrinsic property of a particle, like mass and
charge. The spin angular momentum magnitude a for the
electron is expressed in terms of a single quantum number
(spin quantum number), s = ½ (for H-atom) :
a ö § ö
Y r
a is quantized in space as
described in the figure:
Vt can have two orientations
relative to a z-axis, specified by
the spin magnetic quantum
number ms = Ú½. The z-
Y
component of is :
= Ú2 30
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a3 %)$ 00 How many sets of quantum numbers
are possible for an electron for which (a) n=1, (b) n=2, (c)
n=3, (d) n=4, and (e) n=5 ? Check your results to show
that they agree with the general rule that the number of
sets of quantum numbers for )) 4-)
44
To examine the motions of electrons that lie deep within
multi-electron atoms, one needs to consider the x-ray
spectrum of atoms, shown in the figure below:
The x-ray spectrum has two parts: $ G # ,!
#.&
!
) !
.. ,!
#.& $%1 #
) , *
-%1
$ -
$ !#
#1 .,#&,
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G'A+
D 2
Ȝ 2,&
8
3
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aharply defined cutoff wavelength (8&) is a prominent feature
of the continuous x-ray spectrum. Consider an electron
accelerated through a potential difference of ¨V (x-ray tube
voltage) , hitting a target atom. The electron¶s initial kinetic
energy is K = e ¨V. The electron loses its kinetic energy by
an amount ¨K = hf, which appears in the form of x-ray
photon energy (Bremsstrahlung: Breaking radiation). ¨K can
have any value from 0 to K. Thus the emitted x-rays can
have any value for the wavelength above ȜMVN in the
continuous x-ray spectrum. Thus
!
ö )? ö
?
!
? ö
Ȝ , D
40
3
| 3
|
# # !&!&" +
The peaks in the x-ray spectrum have wavelengths
characteristic of the target element in the x-ray tube and
hence they form the ?, -. When
a high energy (K = e ¨V, ¨V = x-ray tube voltage) electron
strikes a target atom and knocks out one of its electrons
from the inner shells with energy Em (| Em | K, m = integer),
the vacancy in the inner shell is filled up by an electron
from the outer shell (energy = En, n = integer).
:3/Ô ;
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/Ô/ÔÔ :/
3
| 3
|
A K3 x-ray results due to the transition of the electron from
L-shell to K-shell. A K x-ray results due to the transition of
the electron from M-shell to K-shell. When the vacancy
arises in the L-shell, an L-series (L3, L , L) of x-rays results.
aimilarly, the origin of M-series of x-rays can be explained.
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HRK-aample Problem 48-1: Calculate the cutoff wavelength
for the continuous spectrum of x-rays emitted when 35-keV
electrons fall on a molybdenum target.
.
+
!
? ö
ö
ö ^
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F,? G3 X-rays are produced in an x-ray tube
by a target potential of 500 keV. Vf an electron makes
three collisions in the target before coming to rest and loses
one-half of its remaining kinetic energy on each of the first
two collisions, determine the wavelengths of the resulting
photons. Neglect the recoil of the heavy target atoms.
a%$+!%
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r
r r
r
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r
r ö ö
r r
r r
r ö ö ö
r r
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F,? G! Electrons bombard a molybdenum
target, producing both continuous and characteristic x-rays. Vf
the accelerating potential applied to the x-ray tube is 50.0
kV, what values of (a) ȜMVN (b) ȜKȕ (c) ȜK3 result ? The
energies of the K-shell, L-shell and M-shell in the
molybdenum atom are ±20.0 keV, ±2.6 keV and -0.4 keV,
respectively.
r ^
r ^
r ^
r
3
3
r
3
r r r Ô
3
r
r
r r Ô
| | 3 63
3333
) ¶s observation on the characteristic K3 x-rays shows
a ) between the frequency (f) of the K3 x-rays and
the atomic number (Z) of the target element in the x-ray
tube:
f ö §
a
:3 a
!
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) ;.
?6B±b)e instead of +Ze, where
b is the screening constant due to the screening effect
of the of the only K-electron.
Frequency of the "3 #
a
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and f
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) G,: A cobalt target is bombarded
with electrons, and the wavelengths of its characteristic x-
ray spectrum are measured. A second, fainter characteristic
spectrum is also found, due to an impurity in the target.
The wavelengths of the K3 lines are 1789 pm (cobalt) and
1435 pm (impurity). What is the impurity ?
m §
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) G,%: A three level laser emits light of
wavelength 550 nm. (a) What is the ratio of population of the
upper level (E2) to that of the lower level (E1) in laser transition, at
300 K? (b) At what temperature the ratio of the population of E2
to that of E1 becomes half?
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F,? GG A ruby laser emits light at wavelength
694.4nm. Vf a laser pulse is emitted for 12ps and the energy
release per pulse is 150mJ.
a) What is the length of the pulse and
b) How many photons are there in each pulse?
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Assume that lasers are available whose
wavelengths can be precisely "tuned" to anywhere in the visible
range - that is, in the range 400 nm < Ȝ < 700 nm. Vf every
television channel occupies a bandwidth of 10MHz,how many
channels can be accommodated within this wavelength range?
aolution:
The lower frequency is
f1=c/ Ȝ1 =4.29 x 1014 Hz
The higher frequency is
f2=c/ Ȝ2 =7.50 x 1014 Hz
The number of signals that can be sent in this range is
(f2-f1)/10 = 3.21 x 107
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