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© L. Visscher (2011)
Basic Theory
Dirac (1929)
The general theory of quantum mechanics is now almost
complete, the imperfection that still remain being in
connection with the exact fitting in of the theory with
relativistic ideas. These give rise to difficulties only when
high speed particles are involved, and are therefore of
no importance in the consideration of atomic and
molecular structure and ordinary chemical reactions in
wich it is, indeed, usually sufficiently accurate if one
neglects relativity variation of mass with velocity and
assumes only Coulomb forces between the various
electrons and atomic nuclei.
2
Visible Relativistic Effects
Non-relativistic gold is silver
The 5d-6s transition is shifted from the UV to the visible part of the spectrum
by relativistic effects
6s
6s
Non-Relativistic Relativistic
5d 5d
1
S0 "1D2 1
D2 "3 P2
Lifetime 0.75 s Lifetime 110 s
! !
The hydrogenic atom
The exact non-relativistic energy Z2
NR
E =" 2
2n
6
Day 1: Basic theory, qualitative discussion
Basic Theory
Special relativity
The Dirac equation
Relation to quantumelectrodynamics
Treatment of the electron-electron interaction
Galilean transformation
Consider 2 coordinate systems that move relative to each
other with a velocity v in the x-direction
Galilean transformation leaves distance invariant
2 2 2
x = x " + vt r12 = ( x1 " x2 ) + ( y1 " y2 ) + (z1 " z2 )
2 2 2
y = y" r12# = ( x1# " x2# ) + ( y1# " y2# ) + (z1# " z2# )
z = z" r12 = r12#
Simple addition of velocities, no speed limit
! dx ! d( x " + vt) dx "
w= = = + v = w" + v
dt dt dt
8
In a galaxy far far away…..
Two rotating double stars A and B
Special relativity
Measurement of c gives a constant value that is
independent of the motion of the coordinate system
r12 r12"
c= =
t12 t12
"
c 2t122 # r122 = c 2t12
"2 # r12"2 = 0
Define a new transformation to satisfy this condition
10
Lorentz transformation
Substitute this ansatz in the unprimed equations and solve
v 2 $1/ 2 v
" = # = (1$ 2 ) %= 2
c c
Lorentz transformation
x = " ( x# + vt #) & ( v # r ")($ %1) )
! y = y# r = r " + v( + $t "+
' v2 *
z = z# Generalize to 3d
& ( v # r ") )
$ v ' t = $ (t" + 2 +
t = " &t # + 2 x#) ' c *
% c (
Time and spatial coordinates transform into each other
4-dimensional space-time coordinate system
!
! Nonrelativistic limit (c → ∞) gives Galileo transformation
11
Special relativity
Postulate 1: All inertial frames are equivalent
12
Relativistic Quantum Mechanics
1905 : STR
Einstein : E = mc2
1926 : QM
Schrödinger equation
1928 : RQM
Dirac equation
1949 : QED
Tomonaga, Schwinger &
Feynman
13
Non-relativistic quantization 1
The nonrelativistic Hamilton function
p2
H = T +V = + q" (r )
2m
Quantization
! #
H " i! ; p " $i!%
#t
#
Hˆ & (r,t) = i! & (r,t)
#t
! ˆ2
Hˆ = $ % + q'ˆ (r)
2m
14
Non-relativistic quantization 2
The nonrelativistic Hamilton function
"2
H =T +V = + q# (r )
2m
" = p $ qA Mechanical (π) and canonical momentum (p)
Principle of minimal electromagnetic coupling
Quantization
#
! H " i! ; p " $i!%
#t
#
Hˆ & (r,t) = i! & (r,t)
#t
! iq! q 2
Hˆ = $ ˆ +
% 2 ˆ ' Aˆ + Aˆ ' %
% ( ˆ + Aˆ 2 + q(ˆ (r)
)
2m 2m 2m
15
Quantization
!
! ˆ ˆ 1 ˆ ˆ
2
H = q" +
2m
{ (
# $ %i!& + qA )}
! 2
2
ˆ + q 2
ˆ 2 + iq! # $ &
ˆ , # $A
ˆ
= q"ˆ %
2m
(
# $& )2m
# $A( 2m
) [(
+
)( )]
16
!
Spin and non-relativistic quantization 2
(! " u)(! " v) = (u " v) + i! " (u # v )
ˆ ! ˆ2 ˆ q2 ˆ 2
H =" # + q$ + A
2m 2m
iq! ˆ ˆ ˆ ˆ q!
+ (
#%A +A%# " & % #ˆ ' Aˆ + Aˆ ' #ˆ
) ( )
2m 2m
ˆ # A (r ) f (r) = "
" ˆ # ( f (r)A (r )) A is a multiplicative operator
! ˆ f (r) # A (r ) + f (r)"
(
= " ) ˆ # A (r ) chain rule
= $Aˆ # "
ˆ f (r) + Bf (r)
( ) Use definition of B
ˆ ˆ ˆ ˆ ˆ q2 ˆ 2 q in atomic units
H = T + q" + iqA # $ + A % & # B
2 2
!
"t
After series expansion of the square root this could provide
relativistic corrections to the Schrödinger Equation
!
Disadvantage : Difficult to define the square root operator
in terms of a series expansion (A and p do not commute).
Not explored much.
19
Relativistic quantization 2
Eliminate the square root before quantization
2
( E " q# ) = m 2c 4 + c 2$ 2
Quantization
2
% " (
'i! # q$ˆ * + = ( m c + c ,ˆ )+
2 4 2 2
!
& "t )
Klein-Gordon Equation
Quantization
"#
! i! = $mc 2 + c% & 'ˆ + q(ˆ #
( )
"t
The Dirac equation
21
22
!
Densities
• Charge density
• Current density
!
j (r,t ) = q" † (r,t ) c# " (r,t ) cα is the relativistic velocity operator
• Continuity relation
!
"#(r,t )
+ $ % j (r,t ) = 0
"t
! 23
%(t) = e Et / i!
24
!
The Dirac Hamiltonian
Hˆ = "mc 2 + c # $ %ˆ + q&
( mc 2 + q& 0 c% z c(% x ' i% y )+
* 2 -
0 mc + q& c(% x + i% y ) 'c% z -
=*
* c% z c(% x ' i% y ) 'mc 2 + q& 0 -
* 2 -
) c(% x + i% y ) 'c % z 0 'mc + q & ,
25
$ a1 '
& )
ik#r & a 2 ) Non-relativistic functional form with constants ai
"(r) = e
&a3 ) that are to be determined
& )
%a 4 (
(E * mc ) a
2
1 * c!k z a 3 * c!k* a 4 = 0 After insertion into time-independent
Dirac equation
(E * mc ) a
2
2 * c!k + a 3 + c!k z a 4 = 0
( )
*c!k z a1 * c!k* a 2 + E + mc 2 a 3 = 0 k± = k x ± iky
*c!k + a1 + c!k z a 2 + ( E + mc ) a
2
4 =0
!
26
!
Free particle Dirac equation
E+ = + m 2 c 4 + c 2 ! 2 k 2
E" = " m 2 c 4 + c 2 ! 2 k 2
!
E = m2 c 4 + c2 p2
cpz pz
a 3 = a1 # a1
mc 2 + m 2 c 4 + c 2 p 2 2mc
p+
a 4 # a1
2mc
Upper components are the Large components
Lower components are the Small components
! 28
Free particle Dirac equation
Wave function for E = E-
a4 = 0
c!k z pz
a1 = a 3 2
# a3
E " " mc "2mc
c!k + p+
a2 = a3 # a 3
E " " mc 2 "2mc
29
30
Quantum Electro Dynamics
Introduce a m-dimensional Fock space F(m)
States are defined by the occupation number vector n
n = n1 , n2 ,…, nm
ni = 0,1
vac = 0, 0,…, 0
!
! n k = !nk
vac vac = 1
31
Second Quantization
Second quantized operators
Creation operator
ai† n1 ,…, ni ,…, nm = 0 (ni = 1)
ai† n1 ,…, ni ,…, nm = Ci n1 ,…,1,…, nm (ni = 0)
ai† vac = 0,…,1,…, 0
Annihilation operator
! ai n1 ,…, ni ,…, nm = Ci n1 ,…, 0,…, nm (ni = 1)
ai n1 ,…, ni ,…, nm = 0 (ni = 0)
ai vac = 0
Define all operators in terms of these elementary operators
m
! ˆ =
! "! aˆ†k aˆl
kl
k ,l =1
32
Fock space Hamiltonian
Positive and negative energy solutions define a Fock space Hamiltonian
33
!
Renormalization
1. Subtract energy from the occupied negative energy
states
Hˆ QED = Hˆ Total " E 0 = Hˆ Total " Hˆ Total
2. Re-interpretation
aˆ †p = bˆp† aˆ p = bˆp
! aˆ!† = bˆ! aˆ! = bˆ!†
34
!
Quantum Electro Dynamics
Positive energy for positrons
!
Total charge is also redefined
QED
Qvac = "e vac Nˆ QED vac
electron positron
states states
35
Dressed particles
The QED Hamiltonian depends on the positive and
negative energy solutions of the Dirac equation. The
Dirac equation depends on the external potential
Common choices
Free particle solutions (Feynman,1948)
Fixed external potential (Furry,1951)
External + some mean-field potential ( fuzzy )
36
Electron-electron interaction
Quantize also the EM-field
37
Electron-electron interaction
Three terms up to order c-2
1
g Coulomb"Breit (1,2) =
r12
1
" 2 c# 1 $ c# 2
c r12
1
"
2c 2 ( )( )
c# 1 $ % 1 c# 2 $ % 2 r12
39
Hydrogenic orbitals
Write orbitals as product of radial and angular (2-spinor
functions)
#" L (r )& 1 # Pn) ( r)*) ,m (+ ,, ) &
% S (= % (
$" (r )' r $ iQn) ( r)*-) ,m (+ ,, )'
! l 0 1 1 2 !2 3 3
! j
1/2 1/2 3/2 3/2 5/2 5/2 7/2
κ -1 1 -2 2 -3 3 -4
s1/2 p1/2
p3/2
d3/2
d5/2
f5/2
f7/2
40
41
42
Orbital stabilisation
Alkali metals
H, Li, Na, K, Rb, Cs, Fr, 119
0.20
0.19
0.18
0.17
ns - orbital energy au
nonrelativistic
0.16
relativistic
0.15
0.14
0.13
0.12
0.11
0.10
0 20 40 60 80 100 120 140
Nuclear Charge
43
0.4 0.9
0.8
0.3
0.7
0.2 0.6
nonrelativistic 0.5
nonrelativistic
0.1
relativistic
0.4 relativistic
relativistic
relativistic
0.0 0.3
0 50 100 150 0 50 100 150
Nuclear Charge Nuclear Charge
44
Orbital contraction
The outermost s-orbital becomes more compact
Alkali metals
7.5
7.0
6.5
6.0
5.5
ns <r> in au
5.0
4.5
4.0
3.5
nonrelativistic
3.0
relativistic
2.5
0 20 40 60 80 100 120 140
Nuclear Charge
45
Orbital expansion
The outermost p- and d-orbitals expand
Group 13
Group 12
5.0 2.0
4.5 1.8
4.0 1.6
3.5
1.4
3.0
nonrelativistic 1.2
2.5 relativistic
1.0 nonrelativistic
relativistic relativistic
2.0 relativistic
0.8
0 50 100 150
20 70 120
Nuclear charge
Nuclear Charge
46
Ln-An contraction
47
Spin-Orbit coupling
Spectroscopy
Energy levels are split
Spin selection rules are broken
Molecular structure
The hybridization that occurs when chemical bonds are
formed makes the effects on structure usually only relevant
when comparing to high-precision experiments
But: bonds to heavy and superheavy elements can be
qualitatively different if SOC is included
πg*
πg,3/2*
πg,1/2*
πu
πu,3/2
πu,1/2
σg
σg,1/2
49
Atomization energies
• Atomic asymptotes are lowered by SO-coupling
• First order perturbation theory
Nonrelativistic
2P
SO-splitting
2P
px
py
pz
3/2
Relativistic
Nonrelativistic
Relativistic
p1/2
p3/2
p3/2
50
Relativistic effect on atomization energies (kcal/mol)
-5
-10
-15
-20
-25
-30
-35
HF HF+G MP2 CCSD CISD CCSD(T)
-10
-20
-30
-40
-50
HF HF+G MP2 CCSD CISD CCSD(T)
0.12
0.1
0.08
0.06
0.04
0.02
0
F2 Cl2 Br2 I2 At2
-0.02
HF HF+G MP2 CCSD CISD CCSD(T)
Atomization energies
• Example: Hydrogen halides
• SO-coupling is mostly quenched in the molecule
• First order perturbation theory
• Strong sigma-pi mixing in ultra-relativistic H117
Nonrelativistic Relativistic
σ*
σ1/2*
π
π3/2
π1/2
σ
σ1/2
54
Atomization Energies
aug-pVTZ
-5
HF
HF+G
De
-10 MP2
in
CCSD
shift
-15 CISD
CISD+Q
CCSD(T)
Relativistic
-20
-25
Vibrational Frequencies
aug-pVTZ
0
HF HCl HBr HI HAt
!e (cm-1)
-50
HF
HF+G
-100 MP2
Relativistic shift in
CCSD
CISD
-150
CISD+Q
CCSD(T)
-200
-250
0.006
HF+G
in
0.004 MP2
shift
0.002 CCSD
0.000 CISD
Relativistic
CISD+Q
-0.002
CCSD(T)
-0.004
-0.006
-0.008