Lecture 11

Approximation Solutions: Multi-e Atoms -

Recap:
We are dealing with solution of the Time Integrated non-relativistic Schrodinger Equation for
real systems. Ideally, the only real system that we can solve completely is the H-atom problem.
The 1e- wavefunction solutions have been labeled as orbitals depending on the value of their
angular momentum quantum number as follows:

l0 : s  orbitals for a given n

l 1 : p  orbitals n 1 2 3 4 . .
l 2 : d  orbitals K L M N . . (shells)

The same principle of exact solutions (wavefunctions & energies) for H-atom extends well for all
1e- systems and we have the solutions for “Hydrogen like” atoms as well. These include, e.g.,
He  , Li 2 , Be3 ,... etc. Similar principles are also true for highly excited atoms that has a single
electron excited to very high n .
Multi-electron atoms: The first of this kind would be the He atom with Z = 2.
One most important aspect to note here is that the Schrodinger Equation cannot be solved exactly.

This is a 3-body problem and the key obstacle is

e2
the e   e  repulsion term . This term in the
r1  r2
Ĥ implies that the two electrons are not independent. If the
electrons were independent, the ionization energy of He would be
 54.4 eV . However, experimental value  24.6 eV (much lower)
The quantum state now is:   r1 , r2     r1 , ,  , r2 , 2 , 2 

electron 1 electron 2
This is a 6 – dimensional wavefunction! Impossible to visualize!
One useful but approximate approach would be to consider each electron to be occupying its
own orbital (with Z = 2), completely independent of each other.

Mathematically,   r1 , r2     r1    r2 
Hydrogenic
wavefunctions Orbitals are one e wavefunctions
But this also essentially amounts to neglecting the electron – electron repulsion and letting us
write the electronic configuration of He as:

1s 2
But, this 1s should not be confused with the 1s of the H– atom.
Now we have another issue:
Electrons are fundamental particles and they are indistinguishable
 we should not be able to distinguish between the two 1s electrons.
But,

  r1 , r2     r1    r2 

We have put labels 1 & 2. Electrons do not care about our coordinate systems &/or labels!
In fact, Pauli showed that if you exchange two identical electrons then the total wave function
must change sign.
(This is the general statement of the Pauli exclusion principle)

i.e.,  1, 2     2,1 ; i.e., our  above

 is not quite correct.

antisymmetric
The origin of this fact of nature (!) has to do with a properly of electrons known as spin.
This was illustrated by Stern and Gerlach in 1921. This took a beam of Ag (silver) atoms (total
orbital ang. mom. is Zero) and passed it through an inhomogeneous magnetic field.

N
It is important to note that the Ag

Ag atoms are deflected only in 2

S directions

Net orbital angular momentum is Zero, then why is it that it is only two possible directions?
 Some “other type” of angular momentum such that only two projections allowed.
 1
But,  2l  1  2  l   cannot be Orbital since it is not an integer!
2
Thus, electrons have some intrinsic property, like angular momentum called spin angular
1
momentum: s 
2
Here below are the some of the important aspects of the multi-electron atoms:
1. Schrödinger equation cannot be solved exactly.

This is due to the electron-electron interaction term

e2
; electrons are not independent.
r1  r2

2. Wavefunction have very high dimensionality. For e.g.

 
Li atom with 3 electrons :   r1 ,1 , 1 , r2 ,  2 , 2 , r3 , 3 , 3 
 
 

Electron 2
Coordinates.

Visualization is an issue.

One way, useful but approximate, is to think of each electron occupying its own orbital (with
Z  2 ).

Mathematically,   r1 , r 2     r1    r 2 

Hydrogenic remember : Orbitals

Orbitals are one e  wavefunctions.

This is saying that we essentially neglect the e   e  repulsion.

We thus write the electronic configuration of He as :

1s 2

However, this 1s should not be thought of as the H – atom 1s !

3. Since electrons are identical particles, there is the matter of Pauli principle which
restricts the types of  that are solutions to Schrödinger equation.

This arises from Electrons are fundamental particles and they are indistinguishable
=> not possible to label

4. Pauli principle has to do with an intrinsic property (fundamental) of spin.

Pauli showed that if you exchange two identical electrons then the total wave function must
change sign.

i.e,  1, 2     2,1

First illustrated by Stern and Gerlach in 1921.

Stern Garlach Experiment

Beam of Ag (silver) atoms (net angular momentum zero) through inhomogeneous magnetic field

Electrons Up Down

1 1
 ms   ,  ; “projections”
2 2

“down” spin “up” spin

5. Electrons are spin 1 particles.

2
 ..  ..

Spin states (wavefunctions).

 1
 1  electron one is “up” or ms  
2
1
 1  electron one is “up” or ms   .
2

You should beware of the term "spin." If one uses the "classical radius of the electron" and the
known total angular momentum of the electron, it is easy to calculate that a point on the equator
of the electron is moving at about 137 times the speed of light! Thus, although we will continue
to use the word "spin" it is really a shorthand for "intrinsic angular momentum."

6. We can think of spin as a sort of angular momentum denoted by “S” and “projections”
by ‘ ms ’.

 In analogy with orbital, l and me

1 1 1
s  ms   ,  .
2 2 2

7. Spin states  spin quantum numbers ; s, ms and spin eigenfunctions.

Thus, in general, total electronic wavefunction :

 total   space  r1 , r 2 ,...., r N    spin  1 , 2 ,...., N , 

 

 total 1, 2,..., N  for N – electron system.

Pauli :  total 1, 2,...., j, k ,..., N    total 1, 2,...., k , j,...., N 

*  total is antisymmetric under exchange of any pair of e 

Now let us look at the analogy :

LˆZ Yl me  ,     ml  Yl me  ,   Spherical Harmonics…

really, LˆZ eiml   ml  eiml

 Associated with energy l   2l  1 values of ml

 i.e., ml : l , l  1, l  2, ..., 0, 1, 2, ..., l  1, l

 i   l 1
e
i l 1
e  il e e  il

Eigenfunction of L̂Z
with eigenvalue  l  1 eigenfunction of L̂Z eigenfunction of L̂Z
eigenvalue:   l  1 eigenvalue  l

Similarly, for spin angular momentum:

Every s   2 s  1 ms states
ms :  s,  s  1,....,0,...., s  1, s

 There must be an operator Ŝ Z of which the eigenstates are the various ms - states with
eigenvalues ms

1
For s  (electron) :  2s  1  2
2

1 1
 ms   ; ms  
2 2

eigenfunction of
Ŝ Z (denoted by    ) eigenfunction of Ŝ Z
(denoted by    )
1 1
eigenvalue:  eigenvalue: 
2 2

“up” spin “down” spin.

Some “internal” “spin coordinate”.

[Remember : spin is independent of r and p .]

 For Helium : 1s 2

 spin part :  1   2   both up

 1   2   both down
But identical e  !  1   2   e1 is up, e2 is down
Cannot tell which
Is up which is down.  1   2   e1 is up, e2 is down.

 with orbital approximation :

 space;  1s 1 1s  2  ; shorthand for

 1s 1  1s  2 
something like :
or  1   2  

 total 1, 2   1s 1 1s  2    1   2 

space spin .

Violates Pauli principle as  total 1,2   total 1,2

For it to follow Pauli principle & indistinguishability, we have to use the form:
 total 1, 2   1s 1 1s  2    1   2     2   1
space spin .

which vanishes at all points!!

 in 1s 2 state, electrons cannot both be up or down.

But,

 total 1, 2   1s 1 1s  2   x  1   2     2   1 

space spin

is correct as :
inter-charge
 1 2   2 1  2 1   1 2
1 and 2
  1 2   2 1
 antisymmetric as required by Pauli.

 In He 1s 2 the electrons have opposite spin projections.

In summary:

 space;  1s 1 1s  2  ; shorthand for

 1s 1  1s  2 
something like :
or  1   2  

 total 1, 2   1s 1 1s  2    1   2 

space spin .

Violates Pauli principle as  total 1,2   total 1,2

For it to follow Pauli principle & indistinguishability, we have to use the form:
 total 1, 2   1s 1 1s  2    1   2     2   1
space spin .

which vanishes at all points!!

 in 1s 2 state, electrons cannot both be up or down.

But,  total 1, 2   1s 1 1s  2   x  1   2     2   1 

space spin

is correct as :
inter-charge
 1 2   2 1  2 1   1 2
1 and 2
  1 2   2 1
 antisymmetric as required by Pauli.
 In He 1s 2 the electrons have opposite spin projections.

Now, we come to the 3 – electron atom lithium (Li)

By Pauli principle, 2 of the electrons go to 1s with spin opposite i.e., 1s 2 . Now, where do we put
the third electron ?

For n=2 we have a choice i.e., 2s or 2p.

In H – atom they were degenerate but not for Li atom !

In fact, E2 s Li  ~
 0.2 a.u. ~  5.44 ev
E2 p Li  ~
 3.64 ev .

 
E 1s 2 2 p1 is higher than E 1s 2 2 s1  by about 1.8 ev .
* Thus, Li configuration should be 1s 2 2s1 .
(Total  1,2,3 should be antisymmetric.)

Degenerate: Orbitals with same energy level!

Theoretically, electrons in same shell possess the same energy.
This is not true for multielectron atoms.
The reason is SHIELDING of outer electrons due to the inner electrons!

Shielding results from repulsion of electrons either in the same shell or inner shell. We will
consider shielding from same shell.

Energies of 3rd Shell: 3s < 3p < 3d

These differences are due to shielding!

 2s or 2p electron will see some effective nuclear charge Zeff e instead of Ze .

But, Zeff is different for 2s and 2p electrons.

Because radial distribution is different:

2s  R20 ; 2 p  R21

since Zeff e  Z    e

 s   p   d  ........ etc.

The s – electrons are more tightly

bound than p – electrons. Thus,
E2 s  E2 p

 Li is 1s 2 2s1 configurations: Valence electron is the 2s1 electron.

For electrons in 3rd shell:

3p is shielded by 3s
3d is shielded by 3s & 3p

Because electrons in 3s shield electrons in 3p from the nucleus, additional energy needed to
maintain electrons in 3p orbital.
Because both 3s/3p shield 3d from nucleus, even more energy needed to maintain electrons in 3d
orbital.
However, note that the energy ordering :

1s 2s 2 p 3s 3 p 4s 3d 4 p 5s 4d ..... Aufbau Principle

which essentially provides the Rules for Filling Orbitals:

1. Lower-energy orbitals fill first.

2. An orbital can hold only 2 electrons with opposite spins (Pauli Exclusion Principle).
1. If 2 or more degenerate orbitals available, 1 electron goes in each until all are half-full
(Hund's Rule).

Hund's rule of maximum multiplicity, often simply referred to as Hund's rule, is a principle,
which states that a greater total spin state usually makes the resulting atom more stable, most
commonly manifested in a lower energy state, because it forces the unpaired electrons to reside
in different spatial orbitals.

A commonly given reason for the increased stability of high multiplicity states is that the
different occupied spatial orbitals create a larger average distance between electrons, reducing
electron-electron repulsion energy.

In reality, it has been shown that the actual reason behind the increased stability is a decrease in
the screening of electron-nuclear attractions. Total spin state is calculated as the total number of
unpaired electrons + 1, or twice the total spin + 1 written as 2s+1.

However, this is only a rough guideline. For certain values of Z these can get reshuffled.

For large Z atoms, relativistic effects need to be considered (not a part of this course) since inner
(core) electrons are moving at speeds appreciable percentage of speed of light (c).