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L. Visscher (2011)
Outline
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
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
Nuclei appear parametrically via their charge, position, and (if applicable) magnetic moment Separate the time and position variables
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.
Later insights
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.
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
) ( E = q +
i j = ij + iijk k
2 1 + H = q i + qA 2m 2 2 2 2 q iq , A = q + A + + 2m 2m 2m
{ (
)}
[(
)(
)]
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)
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
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
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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
J First derivatives with respect to time and position J Linear in scalar and vector potentials
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1) Spin doubles the number of components 2) Relativity doubles the number of components again
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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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(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
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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(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
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
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
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
1 ij H = hi + g 2 i=1 ji i=1
Wave function
(1,, N )
N x 4 components anti-symmetry
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
Zeroth order is the instantaneous electrostatic interactions First correction describes the magnetic interactions Second correction describes retardation of the interaction
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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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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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$ 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
Alkali metals
nonrelativistic relativistic
100
120
140
Nuclear Charge
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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
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
5.0 4.5 4.0 3.5 3.0 2.5 2.0 0 nonrelativistic relativistic relativistic 50 100 Nuclear charge 150
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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)
Chemistry