Cours Relativite PDF

CNRS Universite de Lille 1
Relativistic Quantum Chemistry
Outline
P. 2 / 89
Part I: Introduction
1
Three cornerstones of non-relativistic Quantum Chemistry
The electronic problem
Quantum chemical methods
Which are the relativistic elements?
The limitations of nonrelativistic quantum chemistry
Part II: Relativistic effects

6
Scalar relativistic effects
Illustrations of scalar relativistic effects
The spin-orbit interaction
Illustration of the spin-orbit interaction
Part III: The Dirac equation and four-component calculations
Valerie
Vallet (valerie.vallet@univ-lille1.fr) | CNRS Universite de Lille 1
Outline (2)
P. 3 / 89
Part IV: Two-component relativistic theory

10 How important are the small components?
11 Unitary transformations
12 The Pauli Hamiltonian
13 Regular approximations
14 The Douglas-Kroll-Hess Hamiltonian
15 Summary of approximate 2c-Hamiltonians
Part V: Core approximations

16 Core approximations - Valence only approaches
17 Pseudopotentials
18 Comments on the use of effective core potentials
Part VI: One-component relativistic methods

19 Which spin-orbit operator?
20 Consequences of spin-orbit coupling
21 1c approaches for the treatment of SO-coupling
Valerie
Outline (3)
P. 4 / 89
Part VII: Illustrations of relativistic effects
Part VIII: Final comments
Valerie
Bibliography
P. 5 / 89
Relativistic Quantum Chemistry - The Fundamental Theory of Molecular

Science
M. Reiher, A. Wolf, Wiley (2009)
Introduction to Relativistitc Quantum Chemistry

K. G. Dyall, K. Fgri, Oxford University Press (2007)
Valerie
P. 6 / 89
Part I
Introduction
Which are the relativistic elements?
Valerie

P. 7 / 89
We assume that:
1
molecular systems follow the Born-Oppenheimer approximation

use the concept of Potential Energy Surfaces (PES)
nuclear charge can be described by a finite-size model

(e.g. use of gaussian type basis functions)
electrons move slow enough to be described by a non-relativistic theory
Valerie

P. 8 / 89
The electronic Hamiltonian can be written as
el
= VNN +
X
i
(i ) +
h
1X
(i ) = h0 (i ) + ven (i )
(i , j ); h
g
2
i <j
The problematic term is the two-electron interaction which connects all

electron coordinates. In the absence of any electron-electron interaction the
electronic problem becomes separable, that is, we can solve it for each
electron separately
(r)i (r) = i i (r)
h
The resulting electronic wave function is then written as a Slater determinant

of orbitals
(r1 , rn ) = |1 (r1 )2 (r2 ) n (rn )|
Although the electron interaction can not be ignored, Slater determinants

and orbitals are key ingredients in most quantum chemical methods.
Orbitals are typically expanded in some atom-centered basis
(r) =
Valerie
(r)ci

P. 9 / 89
Many quantum chemical methods employ the variational principle stating

that the expectation value of the Hamiltonian with respect to some trial
function is always above the exact energy (obtained using the exact wave
function)
el |trial i hel |H
el |el i = E exact
htrial |H
The simplest quantum chemical method, Hartree-Fock, employs a simple

Slater determinant as trial function and finds the orbitals which minimizes
the energy. In practice they are found by solving the Hartree-Fock equation
(r)i (r) = i i (r); F = f + Vee

F
mean
{k }
where the Fock operator is an effective one-electron operator containing the

mean field of the other electrons in the molecule. More elaborate methods
such as Configuration Interaction (CI) and Coupled Cluster, employ linear
combination of Slater determinants to capture the full electron correlation.
Still, the majority of todays quantum chemical calculations are based on

density functional theory (DFT) which replaces the complicated electronic
wave function el (r1 , rn ) by the much simpler electron density (r).
Valerie
P. 10 / 89
Los Alamos National Laboratory Chemistry Division
1A
1
H
1
1s
hydrogen
1.008
Be
lithium
beryllium
[He]2s1
6.941
Periodic Table of the Elements
2A
4
Li
3A
5
[He]2s2
[He]2s22p1
boron
9.012
11
12
[Ne]3s1
[Ne]3s2
10.81
13
Na Mg
sodium
22.99
19
magnesium
24.31
20
Ca
potassium
calcium
[Ar]4s1
39.10
37
[Ar]4s2
40.08
55
Cs
[Xe]6s1
cesium
132.9
87
Fr
[Rn]7s1
francium
(223)
5B
23
[Ar]4s23d2
[Ar]4s23d3
44.96
47.88
3B
21
Sc
scandium
38
39
[Kr]5s2
[Kr]5s24d1
88.91
Sr
strontium
[Kr]5s1
4B
22
[Ar]4s23d1
87.62
Rb
rubidium
85.47
Al
56
Ba
[Xe]6s2
barium
137.3
yttrium
Ti
titanium
40
Zr
[Kr]5s24d2
zirconium
91.22
41
chromium
manganese
52.00
42
Nb Mo
[Kr]5s14d4
niobium
92.91
[Kr]5s14d5
molybdenum
95.94
26
Fe
8B
27
Co
28
Ni
[Ar]4s23d5
[Ar]4s23d6
[Ar]4s23d7
[Ar]4s23d8
54.94
55.85
58.93
58.69
43
iron
44
cobalt
45
nickel
46
Tc
Ru
Rh
Pd
technetium
ruthenium
rhodium
palladium
[Kr]5s24d5
(98)
[Kr]5s14d7
101.1
[Kr]5s14d8
102.9
[Kr]4d10
106.4
11B
29
Cu
[Ar]4s13d10
copper
63.55
47
Ag
12B
30
aluminum
[Ar]4s23d10
[Ar]4s23d104p1
Zn
zinc
65.39
48
Cd
26.98
31
Ga
gallium
69.72
49
In
[Kr]5s14d10
[Kr]5s24d10
[Kr]5s24d105p1
107.9
112.4
114.8
silver
cadmium
indium
12.01
[He]2s22p3
nitrogen
14.01
14
15
[Ne]3s23p3
Si
silicon
28.09
32
Ge
[Ar]4s23d104p2
germanium
72.58
50
Sn
[Kr]5s24d105p2
tin
118.7
phosphorus
30.97
33
As
[He]2s22p4
oxygen
16.00
16
[Ne]3s23p4
sulfur
32.07
34
Se
[Ar]4s23d104p3
[Ar]4s23d104p4
74.92
78.96
arsenic
51
selenium
7A
9
[He]2s22p5
fluorine
19.00
17
Cl
[Ne]3s23p5
chlorine
35.45
35
Br
[Ar]4s23d104p5
bromine
79.90
4.003
10
Ne
[He]2s22p6
neon
20.18
18
Ar
[Ne]3s23p6
argon
39.95
36
Kr
[Ar]4s23d104p6
krypton
83.80
52
53
[Kr]5s24d105p3
[Kr]5s24d105p4
[Kr]5s24d105p5
[Kr]5s24d105p6
121.8
127.6
126.9
131.3
Sb
antimony
Te
tellurium
54
Xe
xenon
72
[Xe]6s24f145d2
[Xe]6s24f145d3
[Xe]6s24f145d4
[Xe]6s24f145d5
[Xe]6s24f145d6
[Xe]6s24f145d7
[Xe]6s14f145d9
[Xe]6s14f145d10
[Xe]6s24f145d10
[Xe]6s24f145d106p1
[Xe]6s24f145d106p2
[Xe]6s24f145d106p3
[Xe]6s24f145d106p4
[Xe]6s24f145d106p5
[Xe]6s24f145d106p6
178.5
180.9
183.9
186.2
190.2
190.2
195.1
197.0
200.5
204.4
207.2
208.9
(209)
(210)
(222)
110
111
112
(272)
(277)
89
[Rn]7s26d1
hafnium
actinium
(227)
104
58
Ce
[Xe]6s24f15d1
[Rn]7s25f146d2
rutherfordium
(257)
59
Pr
[Xe]6s24f3
73
Ta
tantalum
105
106
[Rn]7s25f146d3
[Rn]7s25f146d4
Db
dubnium
(260)
60
[Xe]6s24f4
praseodymium
neodymium
90
91
92
Th
[Rn]7s26d2
thorium
232.0
140.9
Pa
[Rn]7s25f26d1
protactinium
(231)
Sg
seaborgium
(263)
61
75
Re
rhenium
107
Bh
[Rn]7s25f146d5
bohrium
(262)
62
76
Os
osmium
108
Hs
[Rn]7s25f146d6
hassium
(265)
63
Nd Pm Sm Eu
cerium
140.1
74
tungsten
144.2
[Rn]7s25f36d1
uranium
(238)
[Xe]6s24f5
promethium
(147)
93
Np
[Rn]7s25f46d1
neptunium
(237)
[Xe]6s24f6
samarium
(150.4)
94
77
Ir
iridium
109
Mt
[Rn]7s25f146d7
meitnerium
(266)
64
79
Au
gold
80
Hg
mercury
65
66
67
Tb
Dy
Ho
terbium
dysprosium
holmium
95
96
97
98
[Rn]7s25f7
[Rn]7s25f76d1
157.3
americium
(243)
curium
(247)
[Xe]6s24f9
158.9
Bk
[Rn]7s25f9
berkelium
(247)
[Xe]6s24f10
162.5
Cf
[Rn]7s25f10
californium
(249)
68
Er
[Xe]6s24f11
[Xe]6s24f12
164.9
167.3
99
Es
[Rn]7s25f11
einsteinium
(254)
82
Pb
lead
83
Bi
bismuth
114
Ds Uuu Uub
darmstadtium
(271)
Gd
[Xe]6s24f75d1
152.0
81
Tl
thallium
[Rn]7s15f146d9
gadolinium
[Xe]6s24f7
europium
Pu Am Cm
[Rn]7s25f6
plutonium
(242)
78
Pt
platinum
erbium
100
fermium
(253)
Po
polonium
85
At
astatine
86
Rn
radon
Uuq
Uuh
116
Uuo
(296)
(298)
(?)
69
Tm
[Xe]6s24f13
thulium
168.9
70
Yb
[Xe]6s24f14
ytterbium
173.0
101
102
[Rn]7s25f13
[Rn]7s25f14
Fm Md No
[Rn]7s25f12
84
iodine
57
88
Actinide Series~
50.94
7B
25
Mn
carbon
[Ne]3s23p2
1s2
6A
8
138.9
La* Hf
[Rn]7s2
Lanthanide Series*
vanadium
6B
24
Cr
[Ar]4s13d5
[He]2s22p2
5A
7
helium
[Xe]6s25d1
lanthanum
Ra Ac~ Rf
radium
(226)
[Ne]3s23p1
4A
6
8A
2
He
mendelevium
(256)
nobelium
(254)
118
71
Lu
[Xe]6s24f145d1
lutetium
175.0
103
Lr
[Rn]7s25f146d1
lawrencium
(257)
element names in blue are liquids at room temperature

element names in red are gases at room temperature
element names in black are solids at room temperature
Valerie

P. 11 / 89
Fairly early one realized that nonrelativisitc theory was unable to explain
certain trends in observed properties of atoms and molecules
Metal-carbon bond length in the group 12 [Rao et al. 1960]
I
I
Non-relativistic QC: bond length should increase from Zn, Cd, to Hg

Experimentally: bond length increases from Zn to Cd and then decreases from
Cd to Hg
The decrease in bond length is due to relativistic effects!
Ionization potentials of the p block elements
Need for a relativistic quantum chemical formalism
Valerie
P. 12 / 89
Part II
Relativistic effects
Scalar relativistic effects
Illustrations of scalar relativistic effects
The spin-orbit interaction
Illustration of the spin-orbit interaction
Valerie
Scalar relativistic effects: hydrogen-like atoms

P. 13 / 89
In atomic units the average speed of the 1s electron is equal to the nuclear
charge
v1s = Z a.u. and c = 137.0359998a.u.
The relativistic mass increase of the 1s electron is thus determined by the

nuclear charge
me
m = me = p
1 Z 2 /c 2
The Bohr radius is inversely proportional to electron mass

a0 =
40 ~2
m
Relativity will contract orbitals of one-electron atoms, e.g.

Au78+ : Z/c = 58% 18% relativistic contraction of the 1s orbital
Valerie
Scalar relativistic effects: polyelectronic atoms

P. 14 / 89
The effect of the other electrons is to screen the nuclear charge
The relativistic contraction of orbitals will increase screening of nuclear

charge and thus indirectly favor orbital expansion.
In practice we find:
s, p
d, f
s, p orbitals : contraction
d, f orbitals : expansion
Valerie
Colour of gold
P. 15 / 89
(n 1)d
ns
The colours of silver and gold are related to

the transition between the (n 1)d and ns
bands. For silver this transition is in the
ultraviolet, giving the metallic cluster. For
gold it is in the visible, but only when
relativistic effects are included.
Valerie
The contrasting neighbors

P. 16 / 89
1064 C
12.5 kJ/mol
9.29 kJ/mol
19.32 g/cm3
426 kS/m
dimer
Mp
Hfus
Sfus
Conductivity
gas phase
-39 C
2.29 kJ/mol
9.81 kJ/mol
13.53 g/cm3
10.4 kS/m
monomer
[Xe]4f 14 5d10 6s1
[Xe]4f 14 5d10 6s2
pseudo halogen
pseudo noble gas
Without relativistic effects mercury would probably not be a liquid at room

temperature !
Valerie
Spin-orbit interaction
P. 17 / 89
SO
1
s [V p]
2m2 c 2
with V = Zr
Z
ss
2m2 c 2 r 3
The spin-orbit interaction is not the interaction between spin and angular
momentum of an electron. An electron moving alone in space is subject to no
spin-orbit interaction !
The basic mechanism of the spin-orbit interaction is magnetic induction:
An electron which moves in a molecular field will feel a magnetic field in its rest
frame, in addition to an electric field. The spin-orbit term describes the interaction
of the spin of the electron with this magnetic field due to the relative motion of the
charges.
This operator couples the degrees of freedom associated with spin and space
and therefore makes it impossible to treat spin and spatial symmetry separately.
SO
i i ;
Spin magnetization : m =
I
I
collinear magnetization: s = mz =
non-collinear magnetization: s = kmk
Valerie
Heavy open-shell molecule: I+

2
I2+ I2+
P. 18 / 89
[C. Van Wullen,

J. Comput. Chem., 2002, 23, 779785]
Energy :=
0 E0h E
0 Eh
Valerie
= +0.001469972 Eh
+0.001469972
Eh
Energy := =
0.001469972
Eh
2+
Excited states of heavy closed-shell molecule: UO2+
2UO
P. 19 / 89
28180.31982230 Eh
= -28180.31982230 Eh
=Energy
28180.31982230
Eh
LDA excitation energies
(3g )g )
1.87 eV (3
(2g(3
1.92 eV (2
)g ) g )
2.42 eV (2
g
(2)g )
...
(2g )
(2 )
Valerie
Energy :=
Eh Eh Eh
=-28180.31982230
28180.31982230
LDA excitation energies
= 28180.319822
1.81 eV (3g )
(3g )
2.01 eV (2g )
(2g )
2.34 eV (2g )
(3g )
(2g )
...
(2g )
(2 )
Spin-orbit coupling in atoms

P. 20 / 89
In the absence of spin-orbit coupling atomic electronic states are characterized

by total orbital angular momentum L and total spin S and denoted as 2S +1 L. With
spin-orbit interaction only the total angular momentum
J = kL S k, kL + S k
is conserved.
The ground state configuration of oxygen is 1s2 2s2 2p4 which in a non-relativistic
framework (LS-coupling) gives rise to three states.
Term
3
P
1
1
D
S
2
0
0
0
J
2
1
0
2
0
Valerie
Level (cm1 )
0.000
158.265
226.977
15867.862
33792.583
Atomic oxygen emissions in atmospheric aurora

P. 21 / 89
Green line
Red line
Transition
S 0 1 D2
1
D2 3 P2
1
Wavelength(A)
5577
6300
Valerie
Type
E2
M1
Lifetime(s)
0.75
110
P. 22 / 89
Part III
The Dirac equation and four-component calculations
Valerie
Construction of the Hamiltonian

P. 23 / 89
Non-relativistic free particle

E
p2
2m
Relativistic free particle

E =
NR
m2 c 4 + c 2 p2 ; h, mc ] or [+mc , i
Connection the relativistic and non-relativistic energy
r
E = mc
1+
p4
p2
p2
2
=
mc
+
+
|{z}
2m2 c 2
2m
8m3 c 2
rest mass
Valerie
{z
kinetic energy
Principle of minimal electromagnetic coupling

P. 24 / 89
[M. Gell-Mann, Nuovo Cimento Suppl., 1956, 4, 848]

Electric and magnetic fields can be expressed in terms of scalar and vector
potentials
A
;B = A
E =
t
The Hamiltonian of a particle interacting with external fields is obtained from
the free-particle Hamiltonian through the substitutions:
p = p qA Electron : q = e
p = p + eA
E E + e
Valerie
The Dirac equation in a molecular field

P. 25 / 89
Classically we have
E + enuc =
A
;B = A
t
with
D = E ; h
D = mc +c (p)+VeN ; VeN = enuc
h
2
L

L

; = I2
=
S

02
S
=
S
-2mc2
02
02
; =
I2
02
where appears the 2 2 Pauli spin matrices
0
x =
1
1
0
, y =
0
i
i
0
1
, z =
0
Valerie
0
1

;
Contributions from the large and small component densities

P. 26 / 89
4c
p (r) = p (r)p (r)

here shown for iodobenzene
The highly local and atomic nature of the small components can be exploited to
significantly reduce the computational cost of 4-component molecular calculations
Valerie
The two-electron interaction

P. 27 / 89
The fully relativistic two-electron interaction requires knowledge of the

complete history of the two moving particles and can only be given as a
perturbation expansion in c 2 :
Coulomb term O (c 0 ) (including spin-same orbit (SSO))

Coul
ij
g
I4 I4
; charge-charge interaction
ri j
Breit term O (c 2 )
Breit
ij
g
I
Gaunt term (including spin-other orbit (SOO))
ijGaunt =
g
I
= gijGaunt + gijgauge
c i c i
c 2 ri j
; current-current interaction
Gauge-dependent term:
gauge
ij
g
Valerie
(c i i )(c i i )rij
2c 2
Physical interpretation of the DCB Hamiltonian

P. 28 / 89
one-body Hamiltonian
c
kinetic energy
Vext
One-body spin-orbit coupling
mc 2
rest mass energy
Two-body Hamiltonian
1
r12
Coulomb interaction
spin-same-orbit interaction
1 1 2
Gaunt:
2 r12
spin-other-orbit interaction
spin-spin interaction
orbit-orbit interaction
1 (1 r12 )(2 r12 )

Gauge dep.:
3
2
r12
Valerie
orbit-orbit interaction
P. 29 / 89
Part IV
Two-component relativistic theory
10 How important are the small components?
11 Unitary transformations
12 The Pauli Hamiltonian
13 Regular approximations
14 The Douglas-Kroll-Hess Hamiltonian
15 Summary of approximate 2c-Hamiltonians
Valerie
Nature of the small components

P. 30 / 89
Reducing computational cost

Use the no-pair approximation
atomic character of the contributions of the S components

one can neglect the multi-center integral block in the S comp. (cost
reduction)
Transforming the 4-component equation to a two-component one

Beware: Do not ignore the non-negligible contributions of the
small-components: L and S are coupled!
Valerie
2-component relativistic Hamiltonian

P. 31 / 89
Starting from the Dirac equation in a molecular field

Vext + mc 2
c ( p)

L
L
=
E
S
S
we look for the formal decoupling of the large and small components.
Two approaches can be distinguished
1
2
c ( p)
Vext mc 2
decoupling through the elimination of the small components

Foldy-Wouthuysen transformation decoupling by a unitary transformation
It can be shown that the two approaches are equivalent; we thus only
consider the unitary transformation
Valerie
Foldy-Wouthuysen transformation
P. 32 / 89
that formally decouples the large and

We look for a unitary transformation U
small components and transforms a 4-spinor to a 2-spinor such that
hLL
hSL
=W
1W
2 = +
U
+
+ =
1+

1+
The first transformation decouples the large and small components
1 =
W
The exact transformation can be written as a product of two transformations
hLS
h++
U=
hSS
0
whereas the second one re-establishes normalization
2 =
W
Valerie
Foldy-Wouthuysen transformation (2)

P. 33 / 89
1 gives (W
HD W
1)
The first transformation W
1

hLL + hLS
+
hSL +
hSS
hLL
hLS
+ hSL + hSS
hLL
+ hLS
hSL +
hSS
hLL

hLS hSL
+ hSS
For exact decoupling, the off-diagonal elements which are Hermitian

conjugates must be zero
hSL + hSS
=
hLL +
hLS
2 , we obtain the hamiltonian for

After applying the second transformation W
the positive-energy states
h++
1+
+
hSL +
hSS
p
hLL + hLS
|
{z
}
1+

(
hLL +
hLS )
1+

[hLL + hLS ]
p
Valerie
1
1+

Foldy-Wouthuysen transformation (3)

P. 34 / 89
The identification of
appears when on considers the application of the
unitary transformation on the wave function
U
L
S

=
+ (L +
S )
S
(
L)
Since we want the 2-components negative energy solutions to be zero:
S =
L
The two-component positive energy solutions take the form:
(L +
S )
(L +

L)
1+

1
1+

1+

These are the large components renormalized by the

operator
Valerie
Coupling of the large and small components

P. 35 / 89
The exact decoupling implies that
S =
L,
= (2mc 2 V + E )1 c ( p)
The coupling is energy dependent no closed form of the coupling operator
In the nonrelativistic limit (c ), the coupling is energy independent
=
1
( p)
2mc
We can rewrite the coupling operator as
1
K (E )c ( p), with K (E ) =
2mc 2
Valerie

1
V E
2mc 2
1
The Pauli Hamiltonian (1)

P. 36 / 89
Using the definition of

we can define a Hamiltonian acting on the large
components only:
(V E )L +
1
V E
( p) 1
2m
2mc 2
V E
1
2mc 2
1
=1+
V E
V E
+
+ ...
2mc 2
4m2 c 4
defining the operator H+ as

1
( p)( p) +
[H+ E ] L = V E +
2m
( p)L = 0
expansion of the bracket in powers of 1/2mc 2 . The validity of this expansion

depends on |V E | being smaller than 2mc 2
1
Making use of the Dirac identity ( u)( v) = (u v)I2 + i u v

2
( p)( p)
( p)(V E )( p)
(V E )p2 + ~ [ (V ) p i (V ) p] f
Valerie
1
( p)(V E )( p) + . . .
4m2 c 2

P. 37 / 89
L acting on the
We now need to normalize the wave function + = O
positive energy components:
1+

Taylor expansion yields
=
=
1
O
2(V E )
1
( p) 1 +
+ . . . ( p) + . . .
8mc 2
2mc 2
1
2
c 4 )
1+
p + O(
8mc 2
1
2
c 4 )
1
p + O(
8mc 2
1+
The normalization transformation yields
H
+O
1 O
L = E O
L = E +
O
2
or by premultiplying by O
1 H
+O
1 + = E O
2 +
O
Valerie

P. 38 / 89
+V +
T
1
4m2 c 2

1
( p)V ( p) Ep2 T p2 (p2 V + V p2 )
+
2

1
2
Ep
+
= E
2 2
4m c
some developments yields:
1 2
( V ) + (V ) + V 2
2
1 2
(p V + V p2 )
2
~2
( p)V ( p)

~2 (V ) + V 2 + ~ (V ) p
Valerie

P. 39 / 89
This is the Pauli Hamiltonian

4
~2 (2 V )
~
Pauli = T + V p
H
+
+ 2 2 (V ) p
8m3 c 2
8m2 c 2
4m c
{z
}|
{z
}
| {z } |
mass-velocity
Darwin
spin-orbit
Mass-velocity term
Relativistic mass correction
r
E = mc
1+
p2
p4
p2
2
= |{z}
mc +
+...
2
2
m c
2m
8m3 c 2
rest mass
{z
kinetic energy
Problem: The mass-velocity terms has no lower bound Pauli Hamiltonian

cannot be used in variational calculations
Valerie

P. 40 / 89
Darwin term
For a point nuclear potential

V =
Z
Z
, V = 3 r, 2 V = 4 Z (r)
r
r
Darwin term
Darwin
~2 Z
(r)
2m2 c 2
it is proportional to the charge density at the nucleus and it therefore never
negative. The Darwin term will never lower the energy.
h
Spin-orbit term
Rewritten as hSO =
The spin-orbit term described the interaction of the spin of the electron with
this magnetic field due to the relative motion of the charges.
This operator couples the degrees of freedom associated with spin and
space, and makes it impossible to treat spin and spatial symmetry separately
Z
s
2m2 c 2 r 3
Valerie
Regular approximations
P. 41 / 89
Exact coupling
=

1
V E
2mc 2
1
Pauli Hamiltonian only valid if |V E | smaller than 2mc 2 . But close to the
nucleus |V E |/2mc 2 > 1
=
1
K (E )c ( p), with K (E ) =
2mc 2
1
K (E )c ( p), with K (E ) =
2mc 2

1
V E
2mc 2
1
Regular approximation: Use instead the 2mc 2 V expansion, since it is

always positive definite for the nuclear potential and always greater than
2mc 2 . In addition since the potential becomes infinite at a point nucleus,
having V in the denominator regularizes the expansion at the nucleus
K (E ) =
2mc 2
2mc 2 V
Valerie

1+
E
2mc 2 V
1
The ZORA Hamiltonian

P. 42 / 89
Zeroth-Order Regular Approximation (ZORA) (renormalization is ignored):
ZORA = V + 1 ( p)
H
2m
2mc 2
( p)
2mc 2 V
the second term can be seen as an effective kinetic energy operator that
goes to the nonrelativistic one when V 0.
Taylor expansion of (2mc 2 V )1
ZORA
H
1
V2
V
( p) 1 +
+
. . . ( p)
2
2m
2mc
4mc 4
1
V +T +
( p)V ( p) . . .
4m2 c 2
=
=
V+
ZORA contains no mass-velocity term, only parts of the Darwin term, but all
spin-orbit interactions arising from the nuclei
Important parts of the scalar relativistic effects are missing
The nuclear potential V in the denominator is best handled on a numerical

grid, so the ZORA Hamiltonian is particularly suited for DFT calculations
(See ADF, or DIRAC packages)
Valerie
Foldy-Wouthuysen transformation for a free particle (1)

P. 43 / 89
We have seen that only expansions in terms of the potential energy rather
than the momentum yield regular operators
Start with the free-particle Foldy-Wouthuysen transformation (Note that

is
2)
renamed R
=
p
c ( p)
= R2 , Ep = m2 c 4 + c 2 p2
Ep + mc 2
Normalization factor is:
A= p
=
1+

Ep + mc 2
O(c 0 )
2Ep
Transformed hamiltonian
0 = Ep
H
0
2V R
2
0
V +R
+ A
[R2 , V ]
Ep

Valerie

2, V ]
[R
2V R
2 A
V +R

P. 44 / 89
Hamiltonian for the positive-energy levels is

0
p + A V + c ( p) V c ( p) A
H++ = E
Ep + mc 2 Ep + mc 2
Expansion in powers of 1/c yields the Pauli Hamiltonian
Pauli = V + T +
H
1
p4
p2 V
V p2
( p)V ( p)
2
4
3
2
2
2
4m c
8m c
8m c
8m2 c 2
While Pauli is singular (no variational treatment), the presence of the

kinematic factors A and (Ep + mc 2 ) regularizes things
Valerie

P. 45 / 89
In large momentum limit (electron close to the nucleus)

I
I
I
I
Ep cp
A 1/2
2 p/p
R
this transformation ensures bound states (variational treatment possible)
Further decoupling by canceling the off-diagonal element

0
+
R
2 , V ]A
H
= A[
=
second transformation with W
2 such as
+
H
=
=
0
0
0
0
H
H
++
+
+

W
W
+H
+H
W
R
2 , V ]AW
W Ep W A[V + R2 V R2 ]A W A[
+ A[
=0
p W
R
2 , V ]A E
V +R
2V R
2 ]AW
A[
exact decoupling imposes:
Ep + E
p W
= A[
]W
A[
R
2 , V ]A + [A[
V +R
2V R
2 ], W
R
2 , V ]AW
W
Valerie
Approximate decoupling: Douglas-Kroll-Hess transf.

P. 46 / 89
Douglas-Kroll-Hess transformation: decoupling in V
Ep + E
p W
]W
A[
R
2 , V ]A + [A[
V +R
2V R
2 ], W
R
2 , V ]AW
A[
|
{z
} |
{z
} |
{z
}
R
2 , V ]A
A[
O(V 1 )
O(V 2 )
O(V 3 )
Transformation of the one-electron Hamiltonian; transformation of the

two-electron integrals is neglected (classical Coulomb potential)
Possible separation of spin-orbit coupling using the Dirac identity
Valerie
Summary of approximate relativistic Hamiltonians

P. 47 / 89
The exact decoupling of the large and small components is generally not
possible and depends on the external potential
Approximate decoupling may lead to highly singular operators (problem for

variational calculations!)
Decoupling significantly reduces computational cost
Relativistic 1-component (scalar) Hamiltonian and its spin-orbit counterpart

can be obtained by elimination of the spin
Any property operator should be subjected to the same transformation!!!

Picture change. If neglected:
I
I
small errors on valence properties

significant ones on nucleus properties!!!
Valerie
Two-component relativistic methods

P. 48 / 89
2c implementations of most quantum chemical methods (like in 4c)

Dirac Hartree Fock (DHF) methods
Post DHF methods: MP2, Coupled-Cluster methods (CC), CISD, CISDTQ,

Full CI
Multi-configuration Self Consistent field
MRCI methods (GAS-CI), IH(FSCC)
Density Functional Theory
Two-component packages
DIRAC http://wiki.chem.vu.nl/dirac/
UTChem, http://utchem.qcl.t.u-tokyo.ac.jp/
ADF http://www.scm.com/
TURBOMOLE http://www.cosmologic.de/
NWCHEM http://www.emsl.pnl.gov/capabilities/computing/nwchem/
Valerie
P. 49 / 89
Part V
Core approximations
16 Core approximations - Valence only approaches
17 Pseudopotentials
18 Comments on the use of effective core potentials
Valerie
Need for frozen core approximations

P. 50 / 89
In the context of chemical applications

Core orbitals are not involved
in heavy elements (second, third transition series, lanthanides, actinides,

superheavy elements...) large number of core orbitals
core orbitals are essentially atomic like in a molecule or material
core orbitals supply a non-local static potential that can be evaluated once in
the calculation
relativistic effects are too a large extent localized in the core region
include relativistic effects in the core potential
treat valence orbitals non-relativistically
Valerie
Hierarchy of core approximations

P. 51 / 89
Correlate the core electrons at a lower level of theory (e.g. MP2)
Include core electrons only at HF level of theory and freeze them in post-HF
treatments
Use atomic orbitals for core electrons (Frozen Core)
Model frozen core by Effective Core Potentials or Pseudopotentials
Advantages of core approximations

Stepwise reduction of computational cost
One must control the accuracy

I
I
I
choose the right core: core-valence separation either on the basis of energetic
(orbital energies) or spatial (shape, radial maxima or expectation values of
orbitals) arguments.
check different sizes of the core
need for all-electron benchmark calculations
Relativistic effects can be included in Effective Core Potentials by suitable

parametrization
Valerie
Valence-only Hamiltonians (1)

P. 52 / 89
Search for an Hamiltonian which acts on the valence electrons
v =
H
nv
X
v (i ) +
h
v (i , j ) + Vcc + Vcpp
g
i <j
v (i ) and gv (i , j ) are the one and two-electron operators

h
Vcc : repulsion between the cores
Vcpp : core polarization potential (CPP)
nv : number of valence electrons explicitely treated

nv = n
N
X
(Z Q )
Standard effective core potential schemes: implicit treatment of relativity

I
I
nonrelativistic kinetic energy operator

inclusion of relativistic effects via parametrization of the effective core potential.
Implicit approximation: atomic core orbitals are not allowed to change upon
molecule formation (transferability)
Valerie
Valence-only Hamiltonians (2)

P. 53 / 89
v (i ) and h
v (i )
Expression of h
v (i ) =
h
1
1
i + Vcv (i ) and gv (i , j ) =
2
rij
Relativistic effects in the parametrization of Vcv (i ), the effective core

potential, which describes the interaction of one valence electron with all
nuclei and cores present.
The molecular pseudopotential is assumed to be a superposition of atomic

pseudopotentials, with the Coulomb attraction between point charges as the
leading term
Vcv (i ) =

N
X
Q
+ Vcv
(~ri ) + . . .
ri
For the core-core term, the point-charge interaction is also the first term:
Vcv (i ) =

N
X
Q Q
+ Vcc
(~r ) + . . .
<
Valerie
Pseudopotentials (1)
P. 54 / 89
Reduce the basis set to describe valence orbitals
Phillips-Kleinman equation (1959) with an effective one-electron Hamiltonian

framework
Fock equation for a valence orbital v
v v = v v +
F
cv c
c 6=v
c ) onto the valence space

Transformation
using a projector (1 P
P
c =
(P
|
ih
|
)
c
c
c
c )Fv v = v v
(1 P
Reduction of the basis set by mixing v and c , thus removing the radial
nodes in the core region
Np v +
X
c 6=v
c )p
v = (Np )1 (1 P
Valerie
c c
(1)
P. 55 / 89
By inserting into equation 1, we obtain
c )Fv (1 P
c )p = v (1 P
c )p
(1 P
Using the so-called generalized Phillips-Kleinman pseudopotential

V
GPK
c Fv Fv P
c + P
c Fv P
c + v P
c
= P
If one assumes the core orbitals c to be also eigenfunctions of the valence

v , P
c ], one gets a simplified pseudo engenvalue
Fock operator, i.e, [F
problem:
(Fv + V PK )p = v p
containing the so-called Phillips-Kleinman pseudopotential
V
PK
(v c ) |c ihc |
c 6=v
Valerie
P. 56 / 89
For nv valence electrons, one substitutes
v
F
nv
X
v (i ) +
F
(i , j )
g
v Ev
c (i )))
((1 P
v v
i <j
c )
(1 P
nc
Y
i
The valence model Hamiltonian reads:
Hv
nc
Y
c (k ))
(1 P
nv
X
i
v (i ) +
F
X
i <j
(i , j )
g
nc
Y
l
nv
nv
X
X
c (i )P
c (j ) . . . + Vcc
c (i )
Ev
P
P
i
i <j
Valerie
c (l ))
(1 P
P. 57 / 89
In this form, we have not achieved computational saving because the core
orbitals are still present
Elimination of the core with a suitable model potential
i
h
c 1 i + Vcv (i )
v (i ) = (1 P
c (k ))Fv (i )(1 P
c (k )) + Ev P
h
2
h
i
c (k ))(1 P
c (k ))g (i , j )(1 P
c (k )(1 P
c (k )) 1
v (i , j ) = (1 P
g
rij
Valerie
Analytical form of pseudopotentials

P. 58 / 89
[L. R. Kahn and W. A. Goddard, J. Chem. Phys., 1972, 56, 2685]

Semi-local expression of a pseudopotential
Vcv
(~ri ) =
L1
X
l +1/2
lj (i ) + VL (ri )
Vlj (ri ) VL (ri ) P
l =0 j =|l 1/2|
with
lj (i ) =
P
j
X
|ljmj ihljmj |
mj =j
Spin-orbit averaged pseudopotential (scalar-relativistic)
Vcv
ri ) =
,av (~
L1
X
l (i ) + VL (ri )
Vl (ri ) VL (ri ) P
l =0
with
l (i ) =
P
l
X
ml =l
Valerie
|lml ihlml |
Analytical form of pseudopotentials (2)

P. 59 / 89
Spin-orbit pseudopotential:
Vcv
ri )
,SO (~
L1
i
X
Vl (ri ) h
l,l 1/2
l Pl ,l +1/2 (l + 1)P
2l + 1
l =1
L1
X
2Vl (ri ) ~
Pl l ~sPl
2l + 1
l =1
with
Vl (ri ) = Vl,l +1/2 (ri ) Vl,l 1/2 (ri )

Gaussian expansion of the radial parts (easy integrals!) - Fitted parameters

in red (cf. pseudopotentials librairies)
Vlj (ri ) =
Aljk rljki exp (aljk ri )
Valerie
Analytical form of pseudopotentials (3)

P. 60 / 89
For large (polarizable cores)...
Core-polarization potential
Vcpp =
1 X ~2
f
2
Electrostatic field and cut-off factor
~f =
X ~ri
3
ri
1 exp e ri
ne
Valerie
X
6=
~r
3
r
2
(1 exp (c r
))nc
, a (1)
Adjustment of the parameters Aljk , nljk
ljk
P. 61 / 89
Shape-adjustment
Take a valence orbital v
Make a nodeless pseudo-orbital

ev
Invert the Schrodinger

equation and obtain the parameters
/ Impossible for large valence space!

/ Not very precise
Valerie
, a (2)
Adjustment of the parameters Aljk , nljk
ljk
P. 62 / 89
Energy-adjustment (Dolg, Stoll, Stuttgart-Koln)

pseudopotentials
AE
Atomic adjustment to total valence energies EIAE ,valence = EIAE Ecore
multitude of chemically relevant electronic configurations/states/levels of

the neutral atom and low-charged ions !
Optimize the parameters with respect to

S=
AE ,valence
wI E I
EIPP ,valence
2
:= min
, Adjustment can be made to any method
currently best method: (average- level) multi-configuration

Dirac-Hartree-Fock reference data based on the Dirac-Coulomb-Breit
Hamiltonian
Valerie
Comments on effective core potentials

P. 63 / 89
Where to get the parameters

In most quantum chemistry programs (GAUSSIAN, NWCHEM, MOLCAS,

MOLPRO, etc...)
http://www.theochem.uni-stuttgart.de/pseudopotentials/index.
en.html
https://bse.pnl.gov/bse/portal
Stuttgart group because

Always prefer the pseudopotentials from the Koln
they are far more accurate!
Valerie
Comments on pseudopotentials (2)

P. 64 / 89
Illustration of the accuracy of the Koln-Stuttgart

pseudopotentials
Valerie
Warnings about DFT and pseudopotentials?

P. 65 / 89
DFT is assuming a local external potential ....
More seriously (Thomas-Fermi expression of the kinetic energy)

1/3
(c + v )1/3 6= c
1/3
+ v
Nevertheless, a lot of people (including myself!) do it with good results
Dont ask me for an in-depth understanding!
Valerie
P. 66 / 89
Part VI
One-component relativistic methods
19 Which spin-orbit operator?
20 Consequences of spin-orbit coupling
21 1c approaches for the treatment of SO-coupling
Valerie
Philosophy of one-component approaches

P. 67 / 89
Split scalar relativistic effects and spin-orbit coupling

In two-component or pseudopotentials we can separate scalar relativistic

effects from spin-orbit coupling
First run a scalar relativistic
Treat spin-orbit coupling a posteriori
Which spin-orbit operator? Pseudopotential

Dont use all-electron spin-orbit hamiltonian (you have pseudo-orbitals)
Choose the spin-orbit pseudopotential that is paired with your scalar

relativistic pseudopotential
Valerie
Which spin-orbit operator? All-electron calculations

P. 68 / 89
Breit-Pauli Hamiltonian
SO
1el
The one-electron term: H
=
Two-electron term:

r~k
e2 ~ X
~
Z
i
pk
k
4m2 c 2
rk3
k
2el =
H
SO

r~kl
e2 ~ X
~
i
(
~
+
2
~
)
pk
k
l
2m2 c 2
rkl3
k 6=l
Z /r 3 divergence when r 0
Dont use it in variational calculations
Valerie
Which spin-orbit operator? All-electron calculations

P. 69 / 89
With DKH Hamiltonian: no-pair spin-orbit Hamiltonian

The one-electron term:
1el
H
SO
X
k
r
Ak
Ak
Ek + mc 2

i ~k
r~k
p~k
rk3
Ak
Ek + mc 2
Ek + mc 2
2Ek
The two-electron term has two contributions:

SO
2el
H

Ak Al
k 6=l
X
k 6=l

Ak Al
i ~k
Ek + mc 2

2i ~k
Ek + mc 2

Valerie
r~kl
rkl3
r~kl
rkl3

p~k

p~l
1
Ek + mc 2
1
El + mc 2
Ak Al

Ak Al
Mean-field approach to spin-orbit coupling

P. 70 / 89
Calculate two-electron contribution (shielding) from a fixed configuration
Effective one-electron integrals
Fock-operator technique
ij
H
mean-field
=
+
SO
1el
h i |H
|j i
X
1
2el |jk ihik |H

2el |kj i hki |H
2el |jk i}
nk {hik |H
k ,fixed {nk }
Valerie
SO
SO
SO
Mean-field approach: atomic approach

P. 71 / 89
Spin-orbit coupling is short-ranged : r 3 behavior atomic approximation
Compute the Mean-Field integrals for each atom separately
Use atomic orbitals and ground-state average occupations

need for atomic natural basis sets
Atomic Mean-Field SO integral approach (AMFI code, Bernd

Schimmelpfennig)
Splitting identical with full SO-operator within a few wave numbers
Available in DALTON, DeMon, Dirac, MOLCAS, ORCA
Valerie
Consequences of spin-orbit coupling

P. 72 / 89
H = Hnr +
X
~iV
Api + B
4
~
4m2 c 2
X
i

~si
~ri
ri3

~pi
Hso (i ) = f (r )~l ~s = f (r ) (lx sx + ly sy + lz sz ) = f (r ) {(l+ s + l s+ ) /2 + lz sz }
non-relativistic term has certain symmetry properties (atom, molecule,

special symmetry group) C2v , D6h . . .-)
3
P, 2 S, 3 , 2 + , 1 B1 , 2 B2u . . .
Scalar relativistic terms keep these properties (blue)

Commute with L2 , Lz et S 2 , Sz for atoms
with L2z et S 2 , Sz for linear molecules
invariant with respect to symmetry operation in the general case
In atoms and linear molecules, spin-orbit operators dont commute with

L2 , Lz et S 2 , Sz
Valerie
Consequences of spin-orbit coupling

P. 73 / 89
In polyatomic molecules, spin functions have special properties

I
I
I
If Cz () rotation around the z-axis is a symmetry operation (H2 O):

[Cz ()]2 = Cz (2) is the identity
For spin functions Cz (2)|i =?|alphai 6= |i
Double group symmetry
Valerie
1c approaches for the treatment of SO-coupling

P. 74 / 89
SR all-electron basis
SR-PP + basis set
1-component HF/MCSCF
Post-HF/Post-MCSCF treatment to include dynamical correlation and SO

coupling
One-electron SO operator singly-excited configurations
Slow convergence of dynamic correlation (single, double, ..., excited

configurations)
Intermediate coupling scheme:
I
I
SO relaxation of valence orbitals is important for heavy main group atoms

dense spectra in transition metals and actinides
Valerie
P. 75 / 89
Treat correlation and spin-orbit coupling together (1-step

approach)
SR-PP + basis set
Spin-orbit
configuration interaction
Double group
symmetry
SO couples various space and spin symmetries large SOCI space
Make use of double group symmetry and Direct CI
COLUMBUS http://www.univie.ac.at/columbus/
Valerie
Treat correlation and SO in a 2-step fashion

P. 76 / 89
SR-PP + basis set
electron correlation
DFT or WFT correlated method
1) Couple the correlated spin-free states
2) Small SOCI with an effective Ham.
MOLCAS, MOLPRO
EPCISO
Since SO converges faster (small CI space)
MOLCAS (RASSI module) http://www.teokem.lu.se/molcas/
MOLPRO (MRCI module) http://www.teokem.lu.se/molcas/
EPCISO (interface with MOLCAS)valerie.vallet@univ-lille1.fr
Valerie
P. 77 / 89
Part VII
Illustrations of relativistic in chemistry: more common
than you thought
Valerie
Relativistic effects in chemistry

P. 78 / 89
Direct effects
contraction of the core-penetrating orbitals

s orbitals, p1/2 , p3/2 orbitals in core
Energetic stabilization: higher ionization energy, higher electron affinity,

smaller polarizability
Direct effects
indirect effects on d, f , orbitals and valence p orbitals
nuclear charge is shielded to a larger extent because of direct effect on

core-penetrating orbitals (in particular of the semi-core)
relativistic expansion of core non-penetrating orbitals
energetic destabilization
smaller ionization energy, larger polarizability in turn, stabilization of

core-penetrating orbitals in next shell
gold maximum
Valerie
U4+ atomic spectrum

P. 79 / 89
Non Relativistic
Spin-Free
-50
-100
4d
-150
4p
4s
-200
Valerie
Spin-Orbit
Relativistic Effects on Atomic Shell structures

P. 80 / 89
[S. J. Rose et al., J. Phys. B: At. Mol. Phys., 1978, 11, 1171]
Direct (dynamics) and indirect (potential) effects on orbital energies (eV)

Dynamics:
Potential:
Au 6s
Tl 6p1/2
Tl 6p3/2
Lu 5d3/2
Lu 5d5/2
Dirac
Rel
Nonrel
-7.94
-7.97
-5.81
-6.79
-4.79
-5.63
-5.25
-7.32
-5.01
-6.90
Schrodinger
Rel
Nonrel
-6.18
-6.01
-4.58
-5.24
-4.46
-5.24
-4.74
-6.63
-4.81
-6.63
Direct effects dominate for Au 6s and Tl 6p1/2
Compensation of direct and indirect effects for Tl 6p3/2
Indirect effects dominate for Lu
Valerie
Relativistic effects on molecular structures

P. 81 / 89
[C. L. Collins et al., J. Chem. Phys., 1995, 102, 2024]
Bond lengths in pm, dissociation energies in eV, harmonic frequencies in

cm1
Molecule
CuH
Method
reSCF
reMP2
DeSCF
DeMP2
SCF
MP2
NR
DKH
RECP
DC
Exp
156.9
154.2
154.3
154.1
145.4
142.9
142.9
142.8
146.3
1.416
1.476
1.465
1.477
2.585
2.708
2.696
2.711
2.85
1642
1698
1690
1699
2024
2100
2095
2101
1941
NR
DKH
RECP
DC
Exp
177.9
170.1
170.0
170.0
166.3
158.7
158.4
158.5
161.8
1.126
1.229
1.224
1.233
1.986
2.190
2.189
2.195
2.39
1473
1602
1607
1605
1699
1870
1882
1873
1760
NR
DKH
RECP
DC
Exp
183.1
157.6
157.1
157.0
171.1
149.8
149.5
149.7
152.4
1.084
1.727
1.751
1.778
1.901
3.042
3.075
3.114
3.36
1464
2045
2076
2067
1169
2495
2512
2496
2305
AgH
AuH
Valerie
Effects on chemical reactions

P. 82 / 89
SCF reaction energies in kJ/mol for the reaction XH4 XH2 + H2

Method
NR
RECP
DC
Si
263
261
Ge
190
195
177
Sn
129
102
97
Pb
89
-31
-26
Large relativistic effects in Pb
Stabilization of the 6s and destabilization of 6p decreases sp3 hybridization

in PbH4 , thus making the reaction exothermic
In some systems, spin-orbit coupling can enable crossing between states of

different multiplicities (inter-system crossings)
Valerie
Effects on NMR shieldings

P. 83 / 89
et al., J. Phys. Chem. A, 2011, 115, 56545659]

[P. Hrobarik
Isotropic hydrogen shielding parameters (ppm)
Valerie
Relativity and the Lead-Acid Battery

P. 84 / 89
[R. Ahuja et al., Phys. Rev. Lett., 2011, 106, 018301]
The lead-acid battery reaction

Pb(s) + PbO2(s) + 2 H2 SO4(aq) 2 PbSO4(s) + 2 H2 O(l)
The nonrelativistic (NR), scalar relativistic (SR),

and fully relativistic (FR) energy shifts (in eV) for
the solids involved in the lead-acid-battery reaction.
Values for both M = Sn ( green) and M = Pb (black)
are given.
Electromotoric force in eV
experimental: 2.107 V
average fully relativistic DFT value: + 2.13 V
Valerie
Spin-orbit effects in structural chemistry

P. 85 / 89
Strong influence of SO coupling on heavy element structures

SO makes Ptn clusters flat (n = 25)
In Cs18 Tl8 O6 the system exhibit an open-shell degenerate HOMO within a

scalar relativistic approximation.
With SO coupling a closed-shell electronic system is obtained in accordance
with the diamagnetic behavior of this crystal.
Valerie
P. 86 / 89
Part VIII
Comments
Valerie
Some comments
P. 87 / 89
How to choose between 4c, 2c, 1c + SOCI?

I
I
I
Best method depends on the system studied

Which property are you interested in?
What is the accuracy you are looking for? It depends on whether you look at
chemical reactions, spectroscopy, or molecular properties
Which computational capacities do you have access to?
For closed shell systems, one-component methods work well
Dont use non-relativistically contracted basis sets
As usual correlation is important, esp. as there are often a lot of close lying
states with different correlation effects
There are a lot of PPs, ECPs, AIMPs on the market. If you are not sure,
compare to some all-electron method, perhaps even four-component
An approximate method with a good basis set should be preferable to a

more accurate method with a too small basis set.
Valerie
Summary points
P. 88 / 89
Beware of the importance of relativistic effects

1
The classical examples of relativistic effects in chemistry remain and have

been included in most chemistry textbooks.
One of the oldest examples, which deserves more attention, is the

SO-induced NMR heavy-atom shift.
Investigators continue to discover new examples, such as the heavy-element

batteries.
Catalysis is one of the most important applications of relativistic quantum

chemistry.
The SO effects in structural chemistry have been identified only recently

after technical progress.
Valerie
Further reading
P. 89 / 89
Relativistic Quantum Mechanics

R. E. Moss, Advanced Molecular Quantum Mechanics - An Introduction to Relativistic Quantum Mechanics and
the Quantum Theory of Radiation, Springer Netherlands, 1973
P. Strange, Relativistic Quantum Mechanics with Applications in Condensed Matter and Atomic Physics,
Cambridge Univ. Press, 1998, p. 594
Relativistic Quantum Chemical methods

P. Schwerdtfeger, Relativistic Electronic Structure Theory: Part 1, Fundamentals, ed. P. Schwerdtfeger, Elsevier,
Amsterdam, 2002
K. G. Dyall and K. Fgri, Introduction to relativistic quantum chemistry, Oxford University Press, New York, 2007
M. Reiher and A. Wolf, Relativistic Quantum Chemistry: The Fundamental Theory of Molecular Science,
WILEY-VCH Verlag, 2009
Applications
P. Schwerdtfeger, Relativistic Electronic Structure Theory: Part 2, Applications, ed. P. Schwerdtfeger, Elsevier,
Amsterdam, 2004
P. Pyykko,
Ann. Phys., 2012, 63, 4564
Valerie

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CNRS Universite de Lille 1

Relativistic Quantum Chemistry

Three cornerstones of non-relativistic Quantum Chemistry

The electronic problem

Quantum chemical methods

Which are the relativistic elements?

The limitations of nonrelativistic quantum chemistry

Part II: Relativistic effects

Scalar relativistic effects

Illustrations of scalar relativistic effects

The spin-orbit interaction

Illustration of the spin-orbit interaction

Part III: The Dirac equation and four-component calculations

Part IV: Two-component relativistic theory

Part V: Core approximations

Part VI: One-component relativistic methods

Part VII: Illustrations of relativistic effects

Part VIII: Final comments

Relativistic Quantum Chemistry - The Fundamental Theory of Molecular

Introduction to Relativistitc Quantum Chemistry

Three cornerstones of non-relativistic Quantum Chemistry

The electronic problem

Quantum chemical methods

Which are the relativistic elements?

The limitations of nonrelativistic quantum chemistry

Three cornerstones of non-relativistic Quantum Chemistry

molecular systems follow the Born-Oppenheimer approximation

nuclear charge can be described by a finite-size model

electrons move slow enough to be described by a non-relativistic theory

The electronic problem

The electronic Hamiltonian can be written as

The problematic term is the two-electron interaction which connects all

The resulting electronic wave function is then written as a Slater determinant

Although the electron interaction can not be ignored, Slater determinants

Quantum chemical methods

Many quantum chemical methods employ the variational principle stating

The simplest quantum chemical method, Hartree-Fock, employs a simple

(r)i (r) = i i (r); F = f + Vee

where the Fock operator is an effective one-electron operator containing the

Still, the majority of todays quantum chemical calculations are based on

Los Alamos National Laboratory Chemistry Division

Periodic Table of the Elements

element names in blue are liquids at room temperature

The limitations of nonrelativistic quantum chemistry

Non-relativistic QC: bond length should increase from Zn, Cd, to Hg

Ionization potentials of the p block elements

Need for a relativistic quantum chemical formalism

Scalar relativistic effects

Illustrations of scalar relativistic effects

The spin-orbit interaction

Illustration of the spin-orbit interaction

Scalar relativistic effects: hydrogen-like atoms

The relativistic mass increase of the 1s electron is thus determined by the

The Bohr radius is inversely proportional to electron mass

Relativity will contract orbitals of one-electron atoms, e.g.

Scalar relativistic effects: polyelectronic atoms

The effect of the other electrons is to screen the nuclear charge

The relativistic contraction of orbitals will increase screening of nuclear

The colours of silver and gold are related to

The contrasting neighbors

[Xe]4f 14 5d10 6s1

[Xe]4f 14 5d10 6s2