An introduction to Relativistic Quantum Chemistry

Lucas Visscher VU University Amsterdam

Lucas Visscher - VU University Amsterdam

L. Visscher (2011)

Outline

Day 1: Introduction and foundations

Introduction Dirac equation Relativistic effects

Day 2: All electron methods

4-component methods Perturbation theory of relativistic effects 2-component methods

Day 3: Effective core potentials

The frozen core approximation Model potentials Pseudopotentials

Assumptions in Quantum Chemistry

Born-Oppenheimer approximation

Electronic and nuclear motion can be decoupled Electronic energies for motion around clamped nuclei provide potential energy surfaces for nuclear motion Coupling between surfaces can be studied by perturbation theory

Nuclear charge distribution

Point nucleus approximation Nuclear deformations are treated in perturbation theory

Relativity

The speed of electrons is always far below the speed of light Goal is to find time-independent wave functions (stationary states) Magnetic effects are neglected or treated in perturbation theory

Time-independent Dirac equation

Nuclei appear parametrically via their charge, position, and (if applicable) magnetic moment Separate the time and position variables

(r, t ) H (r, t ) = i t (r, t ) = (r )( t )

(r ) = E (r ) H ( t ) = e Et / i

Time dependent Schrdinger or Dirac equation

Time independent Schrdinger or Dirac equation

Diracs view

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. The fundamental laws necessary for the mathematical treatment of large parts of physics and the whole of chemistry are thus fully known, and the difficulty lies only in the fact that application of these laws leads to equations that are too complex to be solved.

Lucas Visscher ACMM - VU University Amsterdam - 5

Later insights

Pekka Pyykk and Jean-Paul Desclaux (1979)

The chemical difference between the fifth row and the sixth row seems to contain large, if not dominant, relativistic contributions which, however, enter in an individualistic manner for the various columns and their various oxidation states, explaining, for example, both the inertness of Hg and the stability of Hg22+.These relativistic effects are particularly strong around gold. A detailed understanding of the interplay between relativistic and shell-structure effects will form the impact of relativity on chemistry.

Jan Almlf & Odd Gropen (1996)

While the incorporation of these effects sometimes increases the computation labor, the increase is generally reasonable, and certainly much less than in, e.g. the transition from semiempirical to ab initio methods for routine quantum chemistry applications. We predict, therefore, that relativistic corrections in one form or another will be included in the majority of all quantum chemistry calculations before the end of this decade.
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Special relativity
Postulate 1: All inertial frames are equivalent Postulate 2: The laws of physics have the same form in all inertial frames

Lorentz coordinate transformations mix time and space

Postulates hold for electromagnetism (Maxwell relations)
Postulates do not hold for Newtonian mechanics

Develop quantum theory from classical relativistic equations and make sure electron spin is described

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Non-relativistic quantization 1
The nonrelativistic Hamilton function
p2 H = T +V = + q (r ) 2m

Quantization

; p i t H (r, t ) = i (r, t ) t = 2 + q (r ) H 2m
H i
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Non-relativistic quantization 2
The nonrelativistic Hamilton function
2 H =T +V = + q (r ) 2m Mechanical () and canonical momentum (p) = p qA Principle of minimal electromagnetic coupling
Quantization

H i ; p i t H (r, t ) = i (r, t ) t 2 iq q 2 +A 2 + q + A + = ( r ) H A 2m 2m 2m =0 A Coulomb gauge: ( )

Spin and non-relativistic quantization 1

We can, however, also write the the Hamilton function as
2

2m $ % i , j & '+ = 2ij

Quantization

) ( E = q +

i j = ij + iijk k

xyz = zxy = yzx = 1 xzy = zyx = yxz = 1

Kronecker delta and Levi-Civita tensor, Summation over repeated indices

2 1 + H = q i + qA 2m 2 2 2 2 q iq , A = q + A + + 2m 2m 2m

{ (

)}

[(

)(

)]

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Spin and non-relativistic quantization 2

( u)( v) = (u v) + i (u v )
2 q = 2 + q + 2 H A 2m 2m iq q A +A + A +A 2m 2m

)
chain rule

A ( r ) f (r ) = ( f (r )A ( r ) )

A is a multiplicative operator

f (r ) A (r ) + f (r ) A (r ) =

f (r ) + Bf (r ) = A

Use definition of B

2 q q 2 H = T + q + iqA + A B 2 2

in atomic units

Spin in NR quantum mechanics

The Pauli Hamiltonian in two-component form
& 1 2 q2 2 q A Bz ( + q + iqA + 2 2 m 2 ( q ( ( Bx + iBy ) ' 2 ) q ( Bx iBy ) + 2 + 1 2 q2 2 q + + q + iqA + A + Bz 2 2m 2 *

Second derivatives w.r.t. position, first derivative w.r.t. time Linear in scalar, quadratic in vector potential Is not Lorentz-invariant L Ad hoc introduction of spin. No explanation for the anomalous g-factor (ratio of 2 between magnetic moment and intrinsic angular momentum) L No interaction between angular momenta due to the orbital and spin: spin-orbit coupling is relativistic effect
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Relativistic quantization 1
Take the classical relativistic energy expression
2 1/ 2

E q = [ m c + c
2 4 2

" E = mc 2 "

Without EM-fields

Quantization recipe gives 2 4 i = q + m c + c 2 2 t After series expansion of the square root this could provide relativistic corrections to the Schrdinger Equation

Disadvantage : Difficult to define the square root operator in terms of a series expansion (A and p do not commute). Not explored much.
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Relativistic quantization 2
Eliminate the square root before quantization

( E q )

= m 2c 4 + c 2 2

Quantization

2 % ( * = ( m 2c 4 + c 2 2 ) 'i q & t )

Klein-Gordon Equation

J Lorentz invariant L No spin * L (r)(r)dr = f (t )

Charge is conserved, particle number is not

The KG-equation can be used for spinless particles

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Relativistic quantization 3
Define a new type of square root

E q = mc 2 + c

[ i, j ]+ = 2ij
Quantization

[ i , ] + = 0

2 =1

+ q i = mc 2 + c t

The Dirac equation

Suitable for description of one electron - Relativistic kinematics

- Charged spin particle
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The Dirac equation

( r, t ) (mc + c + q ) (r, t ) = i t
2

J First derivatives with respect to time and position J Linear in scalar and vector potentials

J Lorentz invariant and are 4-component matrices

$ 0 y' $ 0 z' $ 0 x' $I 0 ' x = & ) z = & ) =& ) y = & ) 0 0 0 0 I % x ( % ( % z ( % y (

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The Dirac Hamiltonian

= mc 2 + c + q H ( 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 z 0 mc + q , )c ( x + i y )

Four component wave function

1) Spin doubles the number of components 2) Relativity doubles the number of components again

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Charge and current density

Charge density
(r, t ) = q (r, t ) (r, t )

Current density
j (r, t ) = q (r, t ) c (r, t )
c is the relativistic velocity operator

Continuity relation

(r, t ) + j (r, t ) = 0 t

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Free particle Dirac equation

Take simplest case : = 0 and A = 0 Use plane wave trial function

$ a1 ' & ) ik r & a 2 ) (r ) = e &a3 ) & ) %a 4 (

Non-relativistic functional form with constants ai that are to be determined

(E mc ) a (E mc ) a
2 2

1 2

ck z a 3 ck a 4 = 0 ck + a 3 + ck z a 4 = 0

After insertion into time-independent Dirac equation

ck z a1 ck a 2 + E + mc 2 a 3 = 0 ck + a1 + ck z a 2
2 4

( ) + ( E + mc ) a

k = k x iky

=0

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Free particle Dirac equation

Two doubly degenerate solutions

(E

m 2c 4 c22 k 2 ) = 0

E+ = + m 2 c 4 + c 2 2 k 2 E = m 2 c 4 + c 2 2 k 2

Compare to classical energy expression

E = m2 c 4 + c2 p2

Quantization (for particles in a box) and prediction of negative energy solutions

Free particle Dirac equation

Wave function for E = E+

ck z ck + a 2 = 0 ; a 3 = a1 ; a 4 = a1 2 2 E + + mc E + + mc k p << mc cpz
For particles moving with nonrelativistic velocities

pz a 3 = a1 a1 2 mc mc 2 + m 2 c 4 + c 2 p 2 p+ a 4 a1 2 mc

Upper components are the Large components Lower components are the Small components

Free particle Dirac equation

Wave function for E = E-

a4 = 0 ck z pz a1 = a 3 a3 2 2 mc E mc ck + p+ a2 = a3 a3 2 2 mc E mc

Role of large and small components is reversed Application of variational principle is more difficult
M Variational Collapse Minmax optimization instead of straight minimization

Dirac sea of electrons

Negative energy solutions are all occupied Pauli principle applies Holes in this sea of electrons are seen as particles with positive charge: positrons (1933) Infinite background charge QED (Quantum Electrodynamics) to properly account for contribution of negative energy states No-pair approximation
Lucas Visscher ACMM - VU University Amsterdam - 23

2mc2

3 e + 1 e+
L

mc2

-mc2

More than one electron

General form of a time-independent Hamiltonian

1 ij H = hi + g 2 i=1 ji i=1

Wave function

(1,, N )

N x 4 components anti-symmetry

(, i,, j,) = (, j,, i,)

Difference between relativistic and non-relativistic calculations is in the calculation of integrals over h and g Second-quantized form of equations is identical to nonrelativistic theory when using the no-pair approximation

Electron-electron interactions

In molecular calculations:
Coulomb Breit g12 =

Coulomb: diagonal operator 1112 1 = r12 r12 1 2 c1 c 2 Gaunt: off-diagonal operator c r12 1 Retardation 2 ( c1 1 ) ( c 2 2 ) r12 2c

Coulomb, Gaunt and retardation terms

Zeroth order is the instantaneous electrostatic interactions First correction describes the magnetic interactions Second correction describes retardation of the interaction
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The hydrogenic atom

Starting point for the LCAO approach Can be solved by separating the radial and angular variables (see Dyall & Faegri or Reiher & Wolf)
# Z 2 % mc r % % % c p $ &# L & # L & r r () ( % () ( c p (% (% ( = E% ( ( % S ( Z (% S 2 mc (% ( r) ( % (r) ( r '$ ' $ '

The exact solutions help in devising basis set approaches and in understanding the chemical bonding in the relativistic regime

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The hydrogenic atom: Energies

The exact non-relativistic energy The exact relativistic energy

2 Z E NR = 2 2n

# % % Z /c 2 E = mc / 1 + $ 2 1 Z % 2 n j + ( j + 1/2) 2 % & 2 c

'2 % % ( % % )

Spin-orbit couping :

j=ls
Energy depends on orbital and spin variables
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The hydrogenic atom: Orbitals

Write orbitals as product of radial and angular (2-spinor functions)

# L (r )& 1 # Pn ( r) ,m ( , ) & % S (= % ( iQ r , r r ( ) ( ) ( ) $ n ' $ ' , m

Solutions to the radial equation

P r Pn ( r) = N n r ( F1 ( r) + F2 ( r)) e

Large component Small component Nonrelativistic

$ E ' = 2 E &1 + ) % 2 mc 2 (
Z2 = 2 < c
2

Qn ( r) = N e r ( F1 ( r) F2 ( r))
Q r n

R Rnl ( r) = N nl e

2 E r l +1

r F ( r)

l j

0 1/2 -1 s1/2

1 1/2 1 p1/2

1 3/2 -2 p3/2

2 3/2 2 d3/2

2 5/2

3 5/2 3 f5/2

3 7/2 -4 f7/2

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-3 d5/2

Orbital stabilization: increase in ionization energy

H, Li, Na, K, Rb, Cs, Fr, 119
0.20 0.19 0.18 0.17
ns - orbital energy au

Alkali metals

0.16 0.15 0.14 0.13 0.12 0.11 0.10 0 20 40 60 80

nonrelativistic relativistic

100

120

140

Nuclear Charge

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Orbital destabilization and spin-orbit splitting

B, Al, Ga, In, Tl, 113
Group 13 0.4

Zn, Cd, Hg, Cn

Group 12 0.9 0.8

0.3

0.7
0.2 nonrelativistic relativistic relativistic 0.0 0 50 100 150 Nuclear Charge

0.6 0.5 0.4 0.3 0 50 100 Nuclear Charge 150 nonrelativistic relativistic relativistic

0.1

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Orbital contraction

The outermost s-orbital becomes more compact

Alkali metals 7.5 7.0 6.5 6.0
ns <r> in au

5.5 5.0 4.5 4.0 3.5 3.0 2.5 0 20 40 60 80 100 120 140 Nuclear Charge nonrelativistic relativistic

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Orbital expansion

The outermost p- and d-orbitals expand

Group 13
Group 12 2.0 1.8 1.6 1.4

5.0 4.5 4.0 3.5 3.0 2.5 2.0 0 nonrelativistic relativistic relativistic 50 100 Nuclear charge 150

1.2 1.0 0.8 20 nonrelativistic relativistic relativistic 70 Nuclear Charge 120

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Ln-An contraction

Ln-An contraction is partly caused by relativistic effects Trend expected from the atomic calculations is confirmed by calculations on LnF, AnF, LnH3 and AnH3 molecules.
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Summary

Relativity

Dirac equation for electron in nonquantized electromagnetic potential Mean-field electronic potential
non-relativistic 2-electron operators before/after finding bound state solutions (a.k. atomic or molecular orbitals)

Higher-order corrections from QED

Chemistry

Scalar relativistic effects

stabilization/destabilization contraction/expansion

Spin-orbit coupling Important for heavy elements