Professional Documents
Culture Documents
1
The orbitalar approach
Slater spin
Mulliken
Combination
Y(1,….N) = Pi fi(i) of Slater
determinants
2
MO approach
A MO is a wavefunction associated with a
single electron. The use of the term "orbital"
was first used by Mulliken in 1925.
E = Si Ei
3
MO approach
Friedrich Hund Charles Alfred Coulson
1896-1997 1910-1974
There is no parameterization.
A subjective choice concerns that the basis
set (always incomplete). The best calculation
(SCF level or after IC) is that providing the6
lowest energy.
Particles are
electrons
Born-Oppenheimer
approximation
1927
Operator acting on e
Julius Robert Oppenheimer
Max Born German
(1882-1970)
} Berkeley- Los alamos
1904 –1967
H = [Te +VN-e + Vee] + TN + VN-N
He = [Te +VN-e + Vee] VN-e also acts on N; when N is
Should be a considered as fixed: VN-e then
coupling term becomes an operator acting on e.
e N
Y = PY(e) PY(N) Separation of Y(e) and Y(N)
7
Born-Oppenheimer
approximation
The forces on both electrons and nuclei due to
their electric charge are of the same order of
magnitude; since the nuclei are so much more
massive than the electrons, they must
accordingly have much smaller velocities.
. Nucleon mass / Electron mass = 1835
For the same kinetic energy, when an electron travels meter a
nucleus of hydrogen travels 2.3 cm, that of carbon 6.7
millimeters and that of gold 1.7 millimeters. It is then
considered as the movement of nuclei and electrons are
independent, that electrons adapt instantaneously to the
movement of nuclei. It is said that the electrons follow
adiabatically the motion of the nuclei.
8
The adiabatic theorem 1928
A physical system remains in its
instantaneous eigenstate if a given
perturbation is acting on it slowly
enough and if there is a gap
between the eigenvalue and the Vladimir
Max Born German rest of the Hamiltonian's spectrum. Aleksandrovich
(1882-1970)
Fock russian
1898–1974
This adiabatic principle is crucial because it allows
us to separate the nuclear and electronic motion,
leaving a residual electron-phonon interaction.
From this point on it is assumed that the electrons
respond instantaneously to the nuclear motion and
always occupy the ground-state of that nuclear
configuration.
9
Vibrations, nuclear motion
Developing U around the equilibrium position (r = req)
gives U(Dr) = U° + U’’(req)Dreq2: The angular frequency is
w = (req/m) ½ depending on the reduced mass m=m1m2(m1+m2)
3N-6 degree of freedom + 3 translations and 3 rotations for the general case.
10
The surface energy obtained
under the Born-Oppenheimer
approximation: adiabatic
surfaces.
These are surfaces that can be achieved step by step from
calculations developed. They may be significant changes in the
characters of orbital obtained. According to an internuclear
distance ionic or covalent change significantly.
In the case of rapidly changing systems (collision dissociations
from excited states), the nature of the orbital can not change and
the Born-Oppenheimer approximation is no longer valid. The state
surface is therefore a surface potential where the same dominant
character is always found. Such surface, called diabatic surface,
is in some region the ground state and for some region an excited
state. Then, there is a jump from an adiabatic surface to another!
The diabatic surfaces are inherently difficult to obtain since 11
calculations lead to the system that is most stable.
PES: Potential Energy Surfaces.
U(d) Covalent
Na+ + Cl-
Diabatic
Adiabatic Na + Cl
Ionic Diabatic
dNa-Cl
An ionic curve “naturally” correlates with ions whereas a
covalent one dissociates to generate radicals. This leads to an
avoided crossing.
12
Finding diabatic surfaces
13
Diabatic- Adiabatic surfaces.
adiabatic diabatic
Process velocity slow fast
Born-Oppenheimer valid Not valid
electrons Adapt Do not
adaptation to the (follow it) (delay to
nuclei motion follow nuclei)
Natural MO May switch Remains
character constant 14
Approximation of
independent particles
Douglas Rayner
Hartree English Vladimir
1897 1958 Aleksandrovich
Fock russian
HHartree= Si Fi 1930
1898–1974
EHartree= Si εi 15
Approximation of
independent particles
Hartree Fock
1927
Fi = Ti + Sk Zik/dik+ Sj Rij
Each one electron operator is the sum of one
electron terms + bielectronic repulsions
Rij is the average repulsion of the electron j upon i.
The self consistency consists in iterating up to
convergence to find agreement between the postulated
repulsion and that calculated from the electron density.
16
This ignores the real position of j vs. i at any given time.
Self-consistency
Given a set of orbitals Yi, we calculate the
electronic distribution of j and its repulsion
with i.
This allows expressing Fi = Ti + Sk Zik/dik+ Sj Rij
and solving the equation to find new Y1i
allowing to recalculate Rij. The process is
iterated up to convergence. Since we get
closer to a real solution, the energy
decreases.
17
Assuming Y= Y1Y2
19
Assuming Y= Y1Y2
Jij, Coulombic integral involved in
two electron pairs
electron 1: Y1 or Y1 interacting with electron 2: Y2 or Y2
When electrons 1 have different spins (or electrons 2 have different spins)
the integral = 0. <aIb>=dij. Only 4 terms are 0 and equal to Jij.
Such expression does not allow two electrons to be in the same state
the determinant is nil when two lines (or columns) are equal;
"No two electrons can have the same set of quantum numbers".
One electron per spinorbital; two electrons per orbital.
“Exclusion principle”
22
Two-particle case
Therefore the Hartree product does not satisfy the Pauli principle. This
problem can be overcome by taking a linear combination of both Hartree
products
24
Obeying Pauli principleY= 1/√ IY1Y2I Slater determinant
26
Obeying Pauli principleY= 1/√ IY1Y2I Slater determinant
Interactions of 2 electrons
27
Unpaired electrons: sgsu
Singlet and triplet states
bielectronic terms
28
Obeying Pauli principleY= 1/√ IY1Y2I Slater determinant
Jj and Kj operators
We need to express the ij bielectronic repulsion as one electron
operator Rj acting on Yj and representing the repulsion with an
average distribution of j.
Rj is the sum of 2 operators Jj and Kj.
29
Slater rules
30
Slater rules
Non zero terms arise from 3 possibilities:
N
32
Electronic energy – total energy
The sum of the energies of all the electrons
contains the ij repulsion twice:
occ occ
i j
ESCF is defined as the energy of YSCF applying Slater rules
Pauli principle occ occ occ
ESCF = <YSCFIHIYSCF> = Shii + S Sj<i(2Jij-Kij)
i i
occ
ETOTAL = ESCF +EN ESCF = EE - Repij = Shii + Repij
i 33
Restricted Hartree-Fock
Closed-shell system: an MO is doubly occupied or
vacant. The spatial functions are independent from the
spin. Assuming k and l with spin a, the expression of
a Fock matrix-element, Fkl, is
occ occ
Fkl = hkl + S [(klIjj)-(klIjj)] - S (klIjj)
J of spin a J of spin b
For DFT, the Janak theorem is a generalization of Koopman’s theorem. J. F. Janak, Phys. 36
Rev. B
18, 7165; J.P. Perdew, R. G. Parr, M. Levy et J. L. Balduz Jr., Phys. Rev. Lett. 23 (1982) 1691.
Koopmans theorem
εk = - IP
Tjalling C.
Koopmans
37
What is wrong with Koopmans
theorem?
The AOs are not “fixed” but relax (“breath”); the Slater exponents
depend on the bielectronic repulsion. The subtraction in the previous
slide suppose no variation. The relaxation is important for polarisable
systems (metals, the work function is generally weak).
Calculating with AOs for the neutral species underestimates the
energy for the ionized species. IP is overestimated by Koopmans
theorem.
38
Cu+ Cu+ Na Na
(Koop.) (exp.) (Koop.) (exp.)
3p 7.28 6.1
3d 1.61 0.79
39
Open-Shell – spin contamination
Let assume that here is one a electron more than b.
For them Fock matrix elements, there is one more exchange term for the
a electrons than for the b’s. The matrix elements are not the same and
solving the secular determinants for a and b independently leads to
different solutions.
fi fi .
The UHF (unrestricted Hartree-Fock method) solves
the secular equation for a and b independently and
obtains different spatial functions for a and b.
This does not allow to have eigenfunctions of the spin
operators. k
k
j
j
i 40
i
ROHF
The same spatial function is taken whatever the
spin is.
Robert K. Nesbet
2e occ 1e occ
F = h + S [( Ijj)-( jI j)] - S ( Ijj)-1/2 ( jI j)
This allowsj eigenfunctions of spinj operators.
42
Correspondence principle 1913/1920
lZ= xpy-ypx
43
Angular momentum
In quantum mechanics angular momentum is defined by an operator
where r and p are the position and momentum operators respectively. In
particular, for a single particle with no electric charge and no spin, the angular
momentum operator can be written in the position basis as
44
Relations in Angular momentum
L2 is the norm and Lx, Ly, Lz are the projections.
[Jx, Jy]= i Jz [Jx, J2]= 0
[Jy, Jz]= i Jx eigenfunctions of J2 are j(j+1)
[Jz, Jx]= i Jy eigenfunctions of Jz are m
45
In atomic units, h =1
Introducing J+ = Jx+iJy and J- = Jx-iJy
J2 = Jx2 + Jy2 + Jz2 = Jz2 + ½ (J+J- + J-J+ )
47
spin
For several electrons: the total spin is the vector sum of the
individual spins.
• For the projection Sz=Ms = Ss ms
• For the norm S2 = S12+S22+2S1S2
S2=[S1z2+S1z+S1-S1+]+[S2z2+S2z+S2-S2+]+[(S1+S2- ++S1-
S2+)+2S1zS2z]
• For 2 electrons, there are 4 spin functions: a(1) a(),
b(1) b(), a(1) b() and a() b(1) that are solutions of Sz.
Are they solution of S2?
48
a(1)a() is solution of S2
a(1) (Sz2+Sz+S-S+) a(2) [1/2]2 + 1/2 + 0 0.75
S-a(1)S+a(2) 0 0
S+a(1)S-a(2) 0 0
total 2
S+a(1)S-b(2) 0 0
total 2
52
S2 as an operator on determinant
S2(D)= Pab(D) + [(na-nb)2 +2na +2nb ] D
Pab is an operator exchanging the spins :a b
na and nb are the # of electrons of each spin
Application:
S2(IaaI) = IaaI+IaaI = -IaaI+IaaI = 0
S2(IabI) = IabI+IabI
S2(IabI-IbaI) = 2 (IabI+IabI)= 2 (IabI-IbaI)
S2(IabI+IbaI) = IabI+IbaI+IabI+IbaI
= -IbaI-IabI+IabI+IabI = 0
53
A single Slater determinant is not
necessarily an eigenfunction of S2
Separation of spatial and spin functions
are a eigenfunction of S2
Not equal