Physical Chemistry II: Quantum Chemistry Lecture 19:Many-electron Atoms & Atomic Term Symbols

Yuan-Chung Cheng yuanchung@ntu.edu.tw 5/3/2011

Courtesy of Prof. Jerry Chen

He: Two-Electron Atom

Attraction

2+ -

Repulsion

He: Two-Electron Atom

Zeff
Attraction

Repulsion

2+

1 < Zeff < 2 Zeff: Effective Nuclear Charge

By the variation method, Zeff is calculated as 1.69

Atomic Orbitals for Many-Electron Atoms

H =E
No analytical solutions even for He because of electron repulsion He and Li atoms can be handled by variation methods Need more practical approach for other atoms!

Hartree-Fock Self-Consistent Field Method

Single-electron wavefunction:

! i (x1 ) : atomic spin orbital x1 : electron variable

Example for 1s:

! 1s (r) = " ca N a e ! Zar/a0

a=1

!1

linear combination of basis functions with variational parameters

!2

N-electron wavefunction: Slater determinants

! 1 (x1 )
!(x1,..., x N ) =

!3

! 2 (x1 ) ! ! N (x1 )

! 1 (x 2 ) ! 2 (x 2 ) ! ! 2 (x 2 ) 1 N! ! ! ! ! 1 (x N ) ! 2 (x N ) ! ! N (x N )

Mean-Field Approximation
Many-electron Hamiltonian:
! 2 N 2 N Ze 2 N !1 N e 2 H =! # "i ! # r + # j=i+1 r # 2me i=1 i=1 i=1 i ij

Many-electron Integrals:
N

kinetic term

nucleus potential

electron replusion

e2 ! 1! 2 !! j ! ! ! 1! 2 !! j ! j=2 r j 1

= =
N

!
j=2

e2 ! 1! j ! 1! j r1 j
2 2

e2 ! "" | ! 1 | | ! j | r d" 1d" 2 j=2 1j

2

# N e 2 | ! j |2 ' % % = " | ! 1 | $! " d" 2 (d" 1 r1 j % j=2 % & )

Mean-field term due to averaged distribution of all other electrons

Mean-Field Approximation
Hartree-Fock Mean-field Hamiltonian:
N ! 2 N 2 N Ze 2 N H =! # "i ! # r + # Vi (ri ) $ # hi 2me i=1 i=1 i=1 i=1 i

| ! j |2 where Vi (ri ) = # e 2 % d" j rij j=i

N

Single determinantal wavefunction leads naturally to the mean-field approximation The approximation allows a factorization of the Hamiltonian into N single-electron problems Given a basis, the theory provides a variational groundstate & optimal atomic orbitals within the single determinant approximation mean-field, no electron correlations N single-electron Schrodinger equations are interdependent requires solving self-consistently via an iterative procedure

Many-electron Model
Hartree-Fock (Self-consistent field, SCF) Method

H =E

Atomic Orbitals for Many-Electron Atoms

The concept of orbital is exact

The use of orbital is just a good approximation

Na Radial Distribution Function for Valance Orbitals

r R(r)
2 2
Core electrons: screening/shielding effect

Penetration effect of the 3s and 3p orbitals

E3 s < E3 p < E3d

Increase screening

Hunds Rule
For degenerate orbitals, electrons occupy them one at a time.
Less likely px py pz

Likely px py pz

Hunds Rule
Smaller electrostatic repulsion?
The electron-electron repulsion does not allow the two electrons getting too close to each other. However, this explanation is now obsolete.

Likely px py pz

Hunds Rule
Exchange energy makes the triplet configuration more stable
Different spins: two electrons do not exchange

px

py

pz

px

py

pz

Same spin: two electrons can exchange

In reality, it has been shown that the actual reason behind the increased stability is a decrease in the screening of electron-nuclear attractions. see Levine

Hunds Rule
Larger electron-nucleus interaction due to less screening when two different orbitals are occupied!
Less likely px py pz

Likely px py pz

Proven by exact QM calculations, see Levine.

Atomic Energy States

C : 1s 2s 2 p

Electron configuration along does not fully specify the state of a many-electron system.

These three arrangements (states) have different energies when electron-electron repulsions are included!
Depending on total angular momentum!

Atomic Energy States -- Terms

The energy of a many-electron state depends on the total orbital angular momentum and total spin angular momentum of the state.

Notations:

L = L1 + L2 + L3 + S = S + S + S +
1 2 3

L: quantum number for total orbital angular momentum l1, l2,: orbital angular momentum quantum numbers for each individual electrons S: quantum number for total spin angular momentum s1, s2,: spin angular momentum for each electrons

L & S are determined by vector addition/subtraction rules.

Example:
p2 (l1 = 1, l2 = 1): L = 2,1, 0

L= 2 =
1 =
= 0

D P S

L = l1 + l2 , l1 + l2 1,, l1 l2
2
0

Example:
p2 (l1 = 1, l2 = 1): L = 2,1, 0

L= 2 =
1 =
= 0

p2f1 (l1 = 1, l2 = 1, l3 = 3)



L=5, 4, 3, 2, 1,

D P S

Addition of Three Angular Momenta

L = l1 + l2 , l1 + l2 1,, l1 l2 L = L + l3 , L + l3 1,, L l3
Lz = l z1 + l z 2 + l z 3
If all l are equal, the minimum is zero, if one l is larger than the others, the minimum is that given by

Adding the first two:

Then add the third one:

l1 l2 l3

(vector sum of all vectors).

Addition of Three Angular Momenta

p2f1 (l1 = 1, l2 = 1, l3 = 3)
L' = 2, 1, 0
L = 5, 4, 3, 2, 1
L = 4, 3, 2
L = 3

Addition of Three Angular Momenta

Degeneracy 2L+1

Number of microstates:

p2f1 (l1 = 1, l2 = 1, l3 = 3)
L = 5, 4, 3, 2, 1
25+1 = 11
24+1 = 9
23+1 = 7
22+1 = 5
21+1 = 3
35

Addition of Three Angular Momenta

Degeneracy 2L+1

Number of microstates:

p2f1 (l1 = 1, l2 = 1, l3 = 3)
L = 4, 3, 2
24+1 = 9
23+1 = 7
22+1 = 5
21

Addition of Three Angular Momenta

Degeneracy 2L+1

Number of microstates:

p2f1 (l1 = 1, l2 = 1, l3 = 3)
L = 5, 4, 3, 2, 1
L = 4, 3, 2
L = 3
3 3 7

35 21 7 63

Total spin angular momentum S for n electrons: S = n/2, n/21, n/22,, 0, for n even S = n/2, n/21, n/22,., 1/2, for n odd
Spin multiplicity = 2S+1

S=0, 2S+1=1, singlet, ms = 0 S=1/2, 2S+1=2, doublet, ms = , - S=1, 2S+1=3, triplet, ms = 1, 0, -1

Total spin angular momentum S for n electrons: S = n/2, n/21, n/22,, 0, for n even S = n/2, n/21, n/22,., 1/2, for n odd

2p

2
S=0 S=1 S=0

Spin multiplicity = 2S+1

singlet, ms = 0 triplet, ms = 1, 0, -1 singlet, ms = 0

 total spin multiplicity exchange energy stablizes many-electron states. slide multiplicity spin multiplicity. total multiplicity total spin multiplicity context multiplicity 2S+1, spin triplet spin triplet s=1, singlet spin singlet s=0

Hunds Rule of Maximum Multiplicity

Hund's first rule states that the lowest energy atomic state is the one which maximizes the total multiplicity for all of the electrons in the open sub-shell.

http://en.wikipedia.org/wiki/List_of_Hund%27s_rules

Russell-Saunders/L-S Term Symbol

Total orbital angular momentum L Total spin angular momentum S Total angular momentum J 2S+1L J
2

J = L+S, L+S-1,.|L-S|

S1/ 2 Double s one-half

Designation: L =0, 1, 2, 3, 4, 5.


S, P, D, F, G, H.

L-S Terms determine energy levels of atomic electronic states for atoms with small spin-orbital coupling (L-S coupling), i.e. not for heavy atoms.

Example 1: a single electron

1s1
2

S1

Hydrogen atom Ground state vs. Excited States

2
2s

S1/ 2

2
2p

P3 / 2
P/2 1

Energy

spin-orbit interaction

1s

S1/ 2

Fine structure of the sodium D line

Energy

Many-electron Atoms
For many-electron system, one may derive the electronic states from the ML, MS, and MJ values.

M L = (ml )i = 0,1,2,.... L
i

M S = (ms )i = 0,1,2,.... S
i

M J = M L + M S = 0,1,2,.... J
These magnetic quantum numbers are easy to determine from electronic configurations we can then derive (L, S, J) from the intervals!

Example 2
1s2

For any filled shell, we just have the state 1 S 0 with L = S = J = 0

Term Symbols & Electronic Configurations

To determine all term symbols in a configuration: 1. List all electronic microstates by filling orbitals with spin specified 2. Calculate ML and MS, then tabulate the number of states belonging to each (ML, MS) 3. Divide states into separate terms based on the bounds of ML and MS 4. Determine term symbols
Core shells are fully occupied and do not give rise to additional states only open shell electrons need to be considered.

Example 3
1s12s1

specifymicrostate termsuperposition indistinguishable

S0
1

S1

S0 + S1
3

Example 4
Carbon: 1s22s22p2
Ignored

Number of possible arrangement is

2p2

6! = 15 2!4!

microstates

M n

Number of spin orbitals Number of electrons

p2 (l1 = 1, l2 = 1): L = 2,1, 0

Carbon: 2p2

Carbon: 2p2 While ML= -22, MS=0 L=2, S=0

Must have a

1D

Carbon: 2p2

While ML= -11, MS= -11 L=1, S=1

1 2 1

Must have a

3P

Carbon: 2p2 While ML= 0, MS= 0 L=0, S=0

1

Must have a GOTCHA!!

1S

too!!

J=2

J=0

Carbon: 2p2

J = 2, 1, 0

A term 2S+1L corresponds to (2L+1)(2S+1) microstates!

2S+1L J

Carbon: 2p2

H0

H 0 + H rep

H 0 + H rep

+ H s .o .

H 0 + H rep

+ H s .o . + H Z

Electronic transitions may occur within the same electronic configuration!

If spin-orbit coupling is larger than the electron-electron repulsion, the scheme of j-j coupling is used instead of L-S coupling. The j-j coupling scheme is more appropriate for heavy transition metal atoms: stronger core potential, faster electron, much more prominent relativistic effects.