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CHEM F111 General Chemistry Lecture 09

Many electron atoms
 Review of lecture 08

• Hydrogenic orbitals
• Radial functions and radial nodes
• Isodensity surfaces, angular nodes
• Probability density and probability distribution
• Electron-spin and selection rules for atomic spectra of
hydrogenic atoms

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Emission spectra of hydrogenic atoms
(revision)
Selection rules:
The allowed electronic transitions in a hydrogenic atom are those in which
the orbital angular momentum quantum number of the atom changes by
one unit. The orbital magnetic quantum number may change at the most by
one unit. The spin magnetic quantum number remains unchanged during
the transition.
Δl=±1, Δml=0,±1, Δms=0
Origin? Conservation of angular momentum:
Photon has spin angular momentum = 21/2ħ corresponding to sproton=1

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Grotrian diagram (revision)

Δl=±1, Δml=0,±1

Δms=0

(Obviously, Δn≠0)
Δn≠0

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Electron spin (revision)

Electron spin described by spin angular momentum quantum number: s = ½

Magnitude of spin angular momentum:
[½(½+1)]½ħ = (3/4)½ħ

Orientation of spin angular momentum

is quantized according to the quantum
number ms:

(In general, ms = -s,-s+1,...,s-1,s)

Consequently, for electron z-component of spin angular moment is ħ/2 or -ħ/2,

corresponding to ms = 1/2 (α) or -1/2 (β), respectively.

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Many electron atoms

Hamiltonian:
2 2 2 2 2
ℏ 2 ℏ 2 2 Ze Ze e
− ∇N− ( ∇ 1 + ∇ 2 +…)− − −…+ +…
2 mN 2 me 4 π ϵ 0 r 1 4 π ϵ0 r 2 4 π ϵ0 r 12
(K.E)N (K.E.)e VNe Vee

The exact solution of Schrödinger equation for atoms with two or more electrons
is impossible. (Vee is the bottleneck – due fast motion of electrons)
However, approximate wavefunctions and energies can be computed with a
tunable accurately.
Consider Vee in approximate way – make separable Hamiltonian

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Pauli principle

When the labels of any two identical fermions (½ integer spin) are exchanged,
the total wavefunction (including spin) changes sign. (ANTI-SYMMETRIC
under exchange)
For Fermions:
ψ( x̄ 1 … x̄ i −1 , x̄ i , x̄ i +1 … x̄ j −1 , x̄ j , x̄ j +1 … x̄ n )=−ψ( x̄ 1 … x̄ i −1 , x̄ j , x̄ i+1 … x̄ j−1 , x̄ i , x̄ j +1 … x̄ n )

When the labels of any two identical bosons (integer spin) are exchanged, the
total wavefunction (including spin) remains the same. (SYMMETRIC under
exchange).

For Bosons:
ψ( x̄ 1 … x̄ i −1 , x̄ i , x̄ i +1 … x̄ j −1 , x̄ j , x̄ j +1 … x̄ n )=ψ( x̄ 1 … x̄ i−1 , x̄ j , x̄ i + 1 … x̄ j −1 , x̄ i , x̄ j +1 … x̄ n )

x̄≡{⃗r , spin}
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Many electron atoms: Orbital
approximation

Wavefunction for many-electron atom: Ψ(1,2,…)

Pauli principle says that the wavefunction should be anti-symmetric with
respect to interchange of space-spin coordinates of any two electrons.
Orbital approximation: Approximate the wavefunction as a product of one
electron functions or orbitals.
Ψ(1,2,…) = ψ1(1)ψ2(2)….. {multiplied by spin parts}*
How correspondingly are we approximating the Hamiltonian? Each orbital
may be thought of as being hydrogen-like with an effective nuclear charge
(effect of average e-e repulsion included).
*anti-symmetry to be ensured

α(ω): for m s =1/2

Spin functions: ∫ α(ω)∗ α(ω) d ω=1=∫ β(ω)∗ β(ω) d ω
β(ω): for m s=−1/ 2 ∫ α(ω)∗ β(ω) d ω=0=∫ β(ω)∗ α(ω) d ω
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Spin-orbitals

Spin-orbital is an orbital multiplied by the electron-spin function.

e.g. Hydrogenic spin-orbitals: State of a hydrogenic atom is completely described by
a hydrogenic spin-orbitals (characterized by four quantum numbers: n, l, ml and ms).
1s_α → n=1, l=0, ml=0, ms=1/2
1s_β → n=1, l=0, ml=0, ms=-1/2
2pz_α → n=2, l=1, ml=0, ms=1/2
2p1_β → n=2, l=1, ml=1, ms=-1/2; and so on.
Hydrogenic spin-orbitals describe the electronic state of the hydrogenic atom
completely.
For a many electron atom, with the wavefunction described using orbital
approximation, no two electrons can have same spin-orbital according to Pauli
principle.

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Form of many electron wavefunctions:
two-electron case
Two electrons in same orbital (spatial function) Φ:
ψ( x̄ 1 , x̄ 2 )=ϕ(⃗r 1 )ϕ(⃗r 2 )×{spin− part }, that is, ψ(1,2)=ϕ(1) ϕ(2)×{spin− part }

Pauli principle: ψ( x̄ 2 , x̄ 1 )=−ψ( x̄ 1 , x̄ 2 ) (MUST BE FOLLOWED!)

How the spin part could be?
α(ω1 )α(ω2 )[≡α(1)α(2)]
OR
β(ω1 )β(ω2 )[≡β(1)β(2)]
(same spin) ?

α(ω1 )β(ω2 )[≡α(1)β(2)]

OR
β(ω1 )α(ω2 )[≡β(1)α (2)]
(opposite spin) ?
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Form of two-electron wavefunction;
paired electrons
What will be the form of the wavefunction?

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Form of two-electron wavefunction;
paired electrons
What will be the form of the wavefunction?
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 )α(1)α (2) ?

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Form of two-electron wavefunction;
paired electrons
What will be the form of the wavefunction?
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 )α(1)α (2) ?

ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 ) β(1) β(2) ?

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Form of two-electron wavefunction;
paired electrons
What will be the form of the wavefunction?
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 )α(1)α (2) ?

ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 ) β(1) β(2) ?

1
ψ( x̄ 1 , x̄ 2 )= ϕ( ⃗r 1 )ϕ( ⃗r 2 ){α (1)β(2)+β(1)α(2)} ?
√2

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Form of two-electron wavefunction;
paired electrons
What will be the form of the wavefunction?
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 )α(1)α (2) ?

ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 ) β(1) β(2) ?

1
ψ( x̄ 1 , x̄ 2 )= ϕ( ⃗r 1 )ϕ( ⃗r 2 ){α (1)β(2)+β(1)α(2)} ?
√2
1
ψ( x̄ 1 , x̄ 2 )= ϕ( ⃗r 1 )ϕ( ⃗r 2 ){α (1)β(2)−β(1) α(2)} ?
√2

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Form of two-electron wavefunction;
paired electrons
What will be the form of the wavefunction?
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 )α(1)α (2) ?

ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 ) β(1) β(2) ?

1
ψ( x̄ 1 , x̄ 2 )= ϕ( ⃗r 1 )ϕ( ⃗r 2 ){α (1)β(2)+β(1)α(2)} ?
√2
1
ψ( x̄ 1 , x̄ 2 )= ϕ( ⃗r 1 )ϕ( ⃗r 2 ){α (1)β(2)−β(1) α(2)} ?
√2

The only form that leads to anti-symmetric wavefunction with respect to

interchange of the coordinates of the electrons is
1
ψ( x̄ 1 , x̄ 2 )= ϕ( ⃗r 1 )ϕ( ⃗r 2 ){α(1)β(2)−β (1)α(2)}
√2

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Anti-symmetry in electronic states with
unpaired electrons
What will be the valid forms of the spatial part of the wavefunction?

The overall wavefunction can be anti-symmetric, if a symmetric spatial part is

multiplied to anti-symmetric spin part and vice versa.

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Anti-symmetry in electronic states with
unpaired electrons
What will be the valid forms of the spatial part of the wavefunction?
ψ(1,2) spatial =[ ϕ i ( ⃗r 1 ) ϕ j ( ⃗r 2 )+ϕ j ( ⃗r 1 ) ϕ i ( ⃗r 2 )] (case A : spatial part symmetric )

The overall wavefunction can be anti-symmetric, if a symmetric spatial part is

multiplied to anti-symmetric spin part and vice versa.

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 Anti-symmetry in electronic states with
unpaired electrons
What will be the valid forms of the spatial part of the wavefunction?
ψ(1,2) spatial =[ ϕ i ( ⃗r 1 ) ϕ j ( ⃗r 2 )+ϕ j ( ⃗r 1 ) ϕ i ( ⃗r 2 )] (case A : spatial part symmetric )

ψ(1,2) spatial =[ϕ i ( ⃗r 1 ) ϕ j ( ⃗r 2 )−ϕ j ( ⃗r 1 ) ϕ i ( ⃗r 2 )] (case B : spatial part anti −symmetric )

The overall wavefunction can be anti-symmetric, if a symmetric spatial part is
multiplied to anti-symmetric spin part and vice versa.

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 Anti-symmetry in electronic states with
unpaired electrons
What will be the valid forms of the spatial part of the wavefunction?
ψ(1,2) spatial =[ ϕ i ( ⃗r 1 ) ϕ j ( ⃗r 2 )+ϕ j ( ⃗r 1 ) ϕ i ( ⃗r 2 )] (case A : spatial part symmetric )

ψ(1,2) spatial =[ϕ i ( ⃗r 1 ) ϕ j ( ⃗r 2 )−ϕ j ( ⃗r 1 ) ϕ i ( ⃗r 2 )] (case B : spatial part anti −symmetric )

The overall wavefunction can be anti-symmetric, if a symmetric spatial part is
multiplied to anti-symmetric spin part and vice versa.

1
Anti-symmetric spin part – only option is: [α (1)β(2)−β(1)α(2)]
√2

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 Anti-symmetry in electronic states with
unpaired electrons
What will be the valid forms of the spatial part of the wavefunction?
ψ(1,2) spatial =[ ϕ i ( ⃗r 1 ) ϕ j ( ⃗r 2 )+ϕ j ( ⃗r 1 ) ϕ i ( ⃗r 2 )] (case A : spatial part symmetric )

ψ(1,2) spatial =[ϕ i ( ⃗r 1 ) ϕ j ( ⃗r 2 )−ϕ j ( ⃗r 1 ) ϕ i ( ⃗r 2 )] (case B : spatial part anti −symmetric )

The overall wavefunction can be anti-symmetric, if a symmetric spatial part is
multiplied to anti-symmetric spin part and vice versa.

1
Anti-symmetric spin part – only option is: [α (1)β(2)−β(1)α(2)]
√2

α(1)α (2)
1
Symmetric spin part – three possibilities: [α (1)β(2)+β(1)α(2)]
√2
β(1)β(2)
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 Anti-symmetry in electronic states with
unpaired electrons
What will be the valid forms of the spatial part of the wavefunction?
ψ(1,2) spatial =[ ϕ i ( ⃗r 1 ) ϕ j ( ⃗r 2 )+ϕ j ( ⃗r 1 ) ϕ i ( ⃗r 2 )] (case A : spatial part symmetric )

ψ(1,2) spatial =[ϕ i ( ⃗r 1 ) ϕ j ( ⃗r 2 )−ϕ j ( ⃗r 1 ) ϕ i ( ⃗r 2 )] (case B : spatial part anti −symmetric )

The overall wavefunction can be anti-symmetric, if a symmetric spatial part is
multiplied to anti-symmetric spin part and vice versa.

1 S=0, MS=0
Anti-symmetric spin part – only option is: [α (1)β(2)−β(1)α(2)]
√2

α(1)α (2)
1
Symmetric spin part – three possibilities: [α (1)β(2)+β(1)α(2)]
√2
β(1)β(2)
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 Anti-symmetry in electronic states with
unpaired electrons
What will be the valid forms of the spatial part of the wavefunction?
ψ(1,2) spatial =[ ϕ i ( ⃗r 1 ) ϕ j ( ⃗r 2 )+ϕ j ( ⃗r 1 ) ϕ i ( ⃗r 2 )] (case A : spatial part symmetric )

ψ(1,2) spatial =[ϕ i ( ⃗r 1 ) ϕ j ( ⃗r 2 )−ϕ j ( ⃗r 1 ) ϕ i ( ⃗r 2 )] (case B : spatial part anti −symmetric )

The overall wavefunction can be anti-symmetric, if a symmetric spatial part is
multiplied to anti-symmetric spin part and vice versa.

1 S=0, MS=0
Anti-symmetric spin part – only option is: [α (1)β(2)−β(1)α(2)]
√2

α(1)α (2) S=1, MS=1

1 S=1, MS=0
Symmetric spin part – three possibilities: [α (1)β(2)+β(1)α(2)]
√2
β(1)β(2) S=1, MS=-1

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Anti-symmetry in electronic states with
unpaired electrons
Thus, the valid wavefunctions are:
1
ψs ( x̄ 1 , x̄ 2 )= N spatial , s [ϕ i ( ⃗r 1 )ϕ j ( ⃗r 2 )+ϕ j ( ⃗r 1 ) ϕi ( ⃗r 2 )][α(1)β(2)−β(1)α (2)]
√2
ψt ( x̄1 , x̄ 2 )( M S = 1)= N spatial , t [ϕi ( ⃗r 1 ) ϕ j ( ⃗r 2 )−ϕ j ( ⃗r 1 ) ϕi ( ⃗r 2 )]α(1)α (2)
1
ψt ( x̄1 , x̄ 2 )( M S = 0)= N [ϕ ( ⃗r )ϕ ( ⃗r )−ϕ j ( ⃗r 1 )ϕi ( ⃗r 2 )][α(1)β(2)+β(1) α(2)]
√ 2 spatial , t i 1 j 2
ψt ( x̄1 , x̄ 2 )( M S =−1)= N spatial ,t [ϕ i (⃗r 1 )ϕ j (⃗r 2 )−ϕ j (⃗r 1 )ϕi (⃗r 2 )]β(1)β(2)

Hamiltonian does not depend on the electron spin, and the energy would depend only on the
spatial part of the wavefunctions.
Thus, there is only one state corresponding to the antisymmetric spin arrangement and is
called singlet.
There are three states (same spatial part, same energy) corresponding to symmetric spin
arrangements and result in a triplet.
What happens to the singlet and triplet wavefunctions when the two electrons approach each
other?

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