4/23/2017

Solution of the Schrodinger Equation for multi -electron

atomic systems cannot be done with perfect precision.
It is because of the repulsion energy terms of the
potential energy of such systems cannot be
handled mathematically with analytical accuracy.
Many Electron Atoms
Approximate (numerical) methods however handle
Chapter 21 such systems numerically with good precision.

Such numerical methods has allowed to consider the

complications brought about in multi-electron systems;
such as indistinguishability of electrons, electron spin,
interaction between orbital & spin magnetic moments.

Time-independent Schrödinger Equation for H atom: Schrödinger Equation in Cartesian coordinates:

Wavefunction ∂ ∂ ∂ ∂2 ∂2 ∂2
∇= + + and ∇ 2 = + +
Separation of variables ∂x ∂y ∂z ∂x 2 ∂y 2 ∂z 2

∂2 ∂2 ∂2
KE ∇ el2 = + 2+ 2
∂x ∂y
2
∂z
KE of the electron
PE

H atom

PE ∇el2
KE
H atom: PE PE
r PE term is spherically r
symmetric; 1/r
H atom He atom

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He Atom – two electron system

The basic idea of Hartree-Fock theory; solving the
∇ el2 ,1 + ∇ el2 , 2 electronic wave function for, hydrogen, which has only
one electron is achieved.
Vel ,1 + Vel , 2 = r12
Imagine we add another electron to hydrogen, H−, then
V1,2 start off by pretending that the electrons don’t interact
V1,2 with each other (i.e. ignore the last term, 1/r12 ).
SE for He atom:
Then the Hamiltonian would be separable, and the total
electronic wavefunction ψ(r1, r2), describing the motions
of the two electrons would just be the product of two
hydrogen atom wavefunctions (orbitals), ψH(r1)ψH(r2).
Insoluble analytically
in closed form.

He Atom – two electron system He Atom – two electron system

∇ el2 ,1 + ∇ el2 , 2 ∇ el2 ,1 + ∇ el2 , 2

Vel ,1 + Vel , 2 Vel ,1 + Vel , 2
V1,2 Soluble analytically Soluble analytically
in closed form. V1,2 in closed form.
 ℏ 2 ℏ 2 2e 2 2e 2   ℏ 2 2e 2 ℏ 2 2e 2 
− ∇ e1 − ∇e2 − − ψ (r1 , r2 ) = Eψ ( r1 , r2 ) − ∇ e1 − − ∇e2 − ψ (r1 , r2 ) = Eψ (r1 , r2 )
4πε 0 r1 4πε 0 r1   2 m 4 πε r 2 m 4 πε 0 r1 
 2me 2me e 0 1 e
Two one-
( +H
H 1 2 )
 ψ (r , r ) = ( E + E )ψ (r , r )
1 2 1 2 1 2 electron SE
 ℏ 2 2e 2 ℏ 2 2e 2   
equations.
− ∇ e1 − − ∇e2 − ψ (r1 , r2 ) = Eψ (r1 , r2 ) H1ψ (r1 , r2 ) + H 2ψ (r1 , r2 ) = E1ψ (r1 , r2 ) + E2ψ (r1 , r2 )
 2me 4πε 0 r1 2me 4πε 0 r1 
ψ (r ) = E ψ (r );
H ψ (r ) = E ψ (r )
H ψHe=ψH(r1)ψH(r2)
1 1 1 1 2 2 2 2

el 2
Orbital Approximation:
As the number of electrons the ri’s increase and so el 1 - distribution
are the number of rij’s.

They, rij’s, are not spherically symmetrical and appears
in the repulsive potential energy terms between
electrons. Such repulsive terms with rij’s cannot be
handled mathematically in an analytical manner, only
numerically.
Therefore a wave function relating all coordinates of
n-electrons as a single function would be impossible.
If there is a way to treat all the electrons as
independent of one another, i.e. with no rij appearing
between electrons, the solution of SE would yield a
wave function for each electron, ψH(r1)ψH(r2).
Now, the effect of electron 1 (el1) on electron 2 (el2)
would be a repulsion that minimize the attractive force
on the el 2 by the positively charged nucleus.
The repulsion would be spherically symmetric!

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SE In the orbital approximation, the many (n) electron

H atom ⇒ wave function is expressed as a product of functions
r where each function depend only on the coordinates
of one electron.

r2 φi (ri) = ‘orbital’ (space part)

r2
e.g. ψHe=ψH(r1)ψH(r2)
r1
This approach makes solution of an n-electron wave
He atom
function from SE, to solving n, one-electron SE
equations.
Concept: Place the second electron in the spherically
symmetric potential field due to nucleus and the spherically
symmetric electron distribution arising from el 1. Solution of which would yield n, φ’s (atomic orbitals)

The functional form of each one electron orbitals φi (ri)

are similar to the H atom orbitals ψ nlml (r , θ , φ ) ; like 1s,
2s, 2p etc., with associated energies; ψHe= φ1(r1)φ2(r2). Z ζ<Z

3/ 2 Zr
H like 1s 1 Z −
a0
of He ion   e ζ<Z
π  a0 
The effect of el 1 on el 2 is like smearing the electrons
H like 1s of e1 uniformly around the atom. It makes the effective
n electron 1 ζ 
3/ 2
−
ζr nuclear charge, ζ < nuclear charge, Z. It would be the
a0
(He) atom   e same for el 1 due to el 2.
π  a0 
Finding ζ is an iterative process, iteration done until
ζ = effective nuclear charge (< Z) felt by the electron. it is self consistent.

el 2

el 1 distribution
to use for Veff calculation. In an n electron atom,

every electron feels the spatially averaged electron

charge distribution by the rest of the (n-1) electrons.
el 1

el 2 distribution
to use for Veff calculation.

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Electron Spin
In multi-electron systems the electron spin plays
an important role in formulating the SE.

Electron spin with has two intrinsic states, two

z-components of spin momentum, as shown below,
s 1 1 1
+ ℏ or - ℏ . sz = ± ℏ . 1 1
2 2 2 ms = + ms = −
2 2
The intrinsic electron spin is a vector s (spin quantum orthogonality
number =1/2). with ms = +1/2 and ms = -1/2 and the
respective spin wavefunctions are α and β
(α & β are orthogonal).
Spin variable

z One electron wave function (a wave function

associated with one electron) will then have
a set of four quantum numbers.
s
n, l , ml and ms i.e.ψ n ,l ,ml ,ms ( r ,θ , φ ).
sz sz Spin function is not dependent on r , θ or φ .
s and it is intrinsic.
1
s 2 = ℏ 2 s (s + 1); s= ψ n ,l , m , m
2 l s

l = ℏ l (l + 1);
2 2
l = 0, 1, ...(n-1)

1sα
n , l , ml , m s So the wave function of which the space part is;

1sβ

must enjoin with its spin part to form the

spatial spin total wave function.
1s wave functions
redefined – spin orbital. energy For He a two electron atom ψ(r1, r2)= ;
The wave function describing an electron in an atomic
orbital has two parts; space and spin parts
e.g, 1s(1)α(1), 1s(1)β(1); an electron ‘labeled’ 1 in
1s space orbital with α spin and electron ‘labeled’ 1 in
1s space orbital with β spin, respectively.

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The indistinguishability of electrons makes

identifying electrons in an atomic system with labels
1sα 1sβ
like 1, 2, .. etc meaningless;
ψ (1, 2) = φ1 (1)α (1)φ2 ( 2)β ( 2)
1s* 1s ψ ( 2,1) = φ1 ( 2)α ( 2)φ2 (1)β (1) symmetric
1 0 interchange of electrons

and also if ψ is expressed as

1sα 1sα ψ ( 2,1) = −φ1 ( 2)α ( 2)φ2 (1)β (1)
is acceptable because ψ 2 would be the same
1s* 1s in both cases.
1 1

Postulate 6 deals with the indistinguishable

character of the electrons in a multi-electron system
after Pauli.

Postulate 6 requires the wavefunction be φ1s (1)α (1)φ1s ( 2)β ( 2) √

anti-symmetric (changes sign) with respect to
φ1s ( 2)α ( 2)φ1s (1)β (1) √
exchange of any two ‘electron labels’
Linear combination of above - a better representation.
A [φ1s (1)α (1)φ1s ( 2)β ( 2) + φ1s ( 2)α ( 2)φ1s (1)β (1)]
But Not anti-symmetric.
A system of many fermions must have a wavefunction
which is antisymmetric under the exchange of any
two fermions in the system.
Anti-symmetric!!

Slater Determinant (total wave function – ground state) spin orbital

φ1s (1)α (1) φ1s (1)β(1)

ψ (1, 2) = A
φ1s ( 2)α ( 2) φ1s (2)β(2)

1 φ1s (1)α (1) φ1s (1)β(1)

ψ (1, 2) =
2 φ1s ( 2)α ( 2) φ1s (2)β(2)

Each column same spin orbital

Each row same electron label

n = # electrons

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total wave function 1s12s1 (total wave function – excited states He)

1 2 3 4

1 φ1s (1)α (1) φ2 s (1)β(1) 1 φ1s (1)α (1) φ2 s (1)α (1)

1 ψ (1, 2) = 2 ψ (1, 2) =
2 φ1s ( 2)α ( 2) φ2 s (2)β(2) 2 φ1s ( 2 )α ( 2) φ2 s (2)α (2)
Anti symmetric character
is in engrained in the spin part 1 φ1s (1)β (1) φ2 s (1)β(1) 1 φ1s (1) β (1) φ2 s (1)α (1)
3 ψ (1, 2) = 4 ψ (1, 2) =
of the total wave function. 2 φ1s ( 2) β ( 2) φ2 s (2)β(2) 2 φ1s ( 2) β ( 2) φ2 s (2)α (2)

3Li (ground state) 3Li (ground state)

If the three electrons are placed in the same orbital If the three electrons are placed in two orbitals (1s 2s)
the total wave function would be; the total wave function would be;

φ1s (1)α (1) φ1s (1)β(1) φ1s (1)α (1) φ1s (1)α (1) φ1s (1)β(1) φ2 s (1)α (1)
1 1
ψ (1, 2, 3) = φ1s ( 2)α ( 2) φ1s (2)β(2) φ1s (2)α (2) ψ (1, 2, 3) = φ1s ( 2)α ( 2) φ1s (2)β(2) φ2 s (2)α (2)
3 3
φ1s (3)α (3) φ1s (3)β(3) φ1s (3)α (3) φ1s (3)α (3) φ1s (3)β(3) φ2 s (3)α (3)

ψ (1, 2, 3) = 0 No wave function at all !! ψ (1, 2, 3) ≠ 0

i.e. three electrons (or more) cannot occupy the

i.e. maximum number of electrons in an atomic
same space orbital, max number of electrons in a
(space) orbital is two; Pauli Exclusion Principle.
space orbital is two; Pauli Exclusion Principle.

The space part of the wave function is hard to Approximate Wave Functions and the Variation
determine in any multi electron system. Method

They are H like functions but are not the same.
H like functions on different atoms are not easy to
integrate as well, (molecules).
The approach in multi-electron systems is to
construct approximate wave functions (trial
functions) that are well behaved.
For many situations it is not practical to obtain a
wave function by analytically solving the wave
equation that describes the system.
Yet, it is possible to perform calculations using the
Variation Theorem starting with a trial function.

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Variation Theorem
Improving the initially constructed trial function ψtrial
Energy associated with a wave function ψ0 (ψ0, true, would improve the calculated E and in it’s limit will
exact wave function) is calculated using; be equal to E0.

∫ψ Hψ dτ
*
0 0
E0 = The trial functions usually contain parameters and
∫ψ ψ dτ
*
0 0 finding the best parameters is the objective of the
variation method.
For any other (trial) wave function ψtrial which is an
approximation (a function constructed to emulate
the state ψ0) the calculated energy would be;
ψ dτ
∫ψ
*
trial H trial
E= ≥ E0
∫ψ ψ trial dτ
*
trial

Variation theorem provides the basis for the variation Illustration: Particle in a Box
method, which states any trial function other than the
true function, ψ0, would give an energy E that is higher Fact: ;true function, ψ0
than the true energy E0.
2 2
A trial function will be constructed with adjustable  =−ℏ d h2 h2
H E1 = = 0 .125
parameters so that it could be varied to improve the 2m dx 2 8ma 2 ma 2
‘trial function’.
An acceptable trial wave function for n=1 state is;
The best parameterized parameters (optimal values)
would give the lowest (minimum) energy
corresponding to the trial function, closer to E0.

In the case of atoms the functions of the form of the

H atom solutions is a good starting point to construct Changing α (parameter) would change the energy
trial wave functions for atoms. estimated.

ψ dτ
∫ψ
*
Set α = 0 and calculate; trial H trial Variation Method
E=
∫ψ ψ trial dτ
*
trial The best value for parameter(s) would yield the lowest
possible energy (minimizes energy) for the trial function.

Variation method allows us to find these ‘optimized

value(s) for the parameter’ - parameterization.

a. Find the expression for energy in terms of the

parameter (s)
b. Generate the expression for energy.
h2 c. Partial differentiation w.r.t. each parameter
ψ 0 ↔ E1 = 0.125 and set the resulting expression to zero.
ma 2
d. Solve for parameters.

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Illustration: Particle in a Box - continuation
a.
b.
c. Completing the integration gives an expression for E.
α=0
The key to success of the
Variation Method is the
selection of a trial function.
α = -0.345
Hartree-Fock theory
Hartree: To solve the Schrödinger equation for an
electron moving in the potential of the nucleus and
all the other electrons, start with a guess for the
trial electron charge density.
Solve n/2 one-particle (one-electron) Schrödinger
equations to obtain n electron wave functions.
Then construct the potential for each wave function
from that of the nucleus and that of all the other
electrons, symmetrize it, and solve the n/2
Schrödinger equations again.
4/23/2017
d.
Differentiating E w. r. t. α and setting it to zero gives
α = -5.74 and -0.345; latter gives the minimum
energy.
h2
ψ 0 ↔ E1 = 0.125
ma 2
h2
ψ trial ↔ E1 = 0.127
ma 2
Self-consistent field theory
An important unsolved problem in QM - how to deal
with indistinguishable, interacting particles.
The basic problem is that if particles interact, that
interaction must represented in the Hamiltonian.
So until we know where the particles are, we can’t
write down the Hamiltonian, and until we know the
Hamiltonian, we can’t tell where the particles are.
Fock: Improved Hartree’s method by using the
properly anti-symmetrized wavefunction (Slater
determinant) instead of simple one-electron
wavefunctions.
Fock’s improvement accounts for the exchange
interaction.
The (HF-SCF) methodology is used for multi electron
systems. This is a variation method. Wherever we
refer to wavefunctions, we assume that they are
expanded in from an appropriate basis set.
Written as an algorithm.
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el 2
HF-SCF Method

el 1 distribution
to use for Veff calculation.
Guess ψ

New Guess improved ψ

ψ
New Guess ψ

Improve old ψ ψSCF el 1

el 2 distribution
to use for Veff calculation.
ψ !!

Solving SE for many electron systems.

Every electron feels the spatially averaged electron
Use orbital approximation and Pauli exclusion principle. charge distribution by the rest of the (n-1) electrons.

Antisymmetric wave function (as Slater determinant)

No rij terms, so spherically symmetric potential exist;

angular part of the orbitals are same as that of H atom.

Every φj is a H like orbital. Radial part φj(r) varies from case to case and the
variation method allows us to find the optimum
parameters of the radial part of wave function.

The functions for φj(r): e.g. acceptable φ(r) for 1s of H

Each φj(r) of the determinant is constructed as a
linear combination of some well behaved (easily
mathematically handled ) basis functions fi(r). 1s
Variational parameters
fi (r ) = N i exp[−ζ i (r / a0 )2 ]
Gaussian function

Variational parameter m=3

suitable
Less suitable
best fit 1s is a sum
of 3 basis functions

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e.g. acceptable φj(r) for 2p.

2p
(error)

Variational parameters

fi (r ) = Ni r exp( −ζ i r / a0 )
m=4

Hartree Fock radial functions can be used to obtain

the radial probability for multi-electron atoms.

ni = # electrons in the subshell. P(r)

In multi-electron atoms
the energy of an orbital
depends on (n + l),
for same (n + l) values,
the higher n value takes
precedence, unlike in
H atom (n only)

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