CHEM F111 Lecture 10

Electronic structure of molecules

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Pilani Campus
Atomic structure
Antisymmetry (Pauli) principle
Hartree Fock SCF theory
Configuration and states
Terms and term symbols
Hunds rules
Spin-orbit coupling
Description of heavy atoms
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Electronic structure of atoms
Now consider the configuration 2p 3p.
How many states are there? 36
Can we classify these as triplets and singlets? Yes
Is there any other basis for classification? Yes. The
total orbital angular momentum quantum number L
What are the possible values? The maximum value is
l
1
+l
2
= 2, the next is l
1
+l
2
-1=1, and the last is l
1
-l
2
= 0
If a set of states is characterized by the values L and S
for the total orbital and spin angular momentum
quantum numbers respectively, how many states are
there? (2L + 1)(2S + 1)
Have we accounted for all the states above? Yes, 15 +
5 + 9 + 3 + 3 + 1 = 36
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Terms and term symbols
States of a many electron atom are characterized
along with the energy, by the total orbital momentum L,
and total spin angular momentum S
These are the conserved quantities
A set of states arising from a given configuration,
having the same L and same S, have the same energy,
and constitute a term.
A term is denoted by
2S+1
L, with L= 0,1,2,3, denoted
as S,P,D,F,terms
Thus for 2p 3p, we have
3
D,
1
D,
3
P,
1
P,
3
S, and
1
S terms
Which of these is of lowest energy? Hunds second
rule: If more than one term of the same max S, then
highest L corresponds to lowest energy. Here
3
D
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Terms and term symbols
How about the 2p
2
configuration? 15 states
Why fewer? Pauli principle places restrictions
What terms arise?
1
D,
3
P, and
1
S, with 5, 9, and 1 states
respectively
Which is of lowest energy?
3
P
Without enumerating all the states, what is the term of
lowest energy that arises from the ground electronic
configuration of N?
4
S
How?
What about 1s
2
2s
2
2p
4
? Same as 2p
2
(why?)
Do closed subshells contribute to L/S? No
For more than two electrons, couple two first, then the
third to the resultant, and so on
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Spin-orbit coupling - Levels
For the lighter atoms (upto Z a little over 40), can treat
this as a small correction
First find the allowed total L and S
Then find the allowed values of J as L+S,L+S-
1,...L-S. This is called Russell-Saunders or L-S
coupling
Set of states arising from a given term with the same
value of J constitutes a term. Degeneracy = 2J+1
Total term (level) symbol
2S+1
L
J,
Hunds third rule
determines term of lowest energy less than half filled
shell : term of lowest J of lowest energy, more than half
filled shell : term of highest J of lowest energy
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Selection Rules
For spectroscopic transitions in many-electron
atoms:
AL = 0, 1
(Al = 1)
AS = 0
AJ = 0, 1 (but J =0 <> J = 0 is forbidden)
For heavier atoms, first couple l and s for
individual electrons to get j values, then couple j
to get J (j-j coupling) why?
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Chemical Bond
Ionic bond: Transfer of electron(s) from one atom to
another, and the consequent attraction between the
ions so formed.
Covalent bond: Two atoms share a pair of electrons.
Concept due to G N Lewis before quantum mechanics
fully developed
Covalent bond and molecular structure:
Wavefunction approach:
Valence Bond Theory
Molecular Orbital Theory
Density Functional Theory: Based on electron density
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Born-Oppenheimer approximation
Treating electronic and nuclear motion simultaneously
difficult. Nuclei much more massive than electrons.
Electronic motions on much faster time scales, adjust
immediately to instantaneous positions of nuclei.
Solve the Schrodinger equation for the electrons for a
series of fixed positions of the nuclei

e
(r
e
;R
n
) = E
e
(R
n
)
e
(r
e
;R
n
)

e
=
e
+ V
ne
+ V
ee
+ V
nn
The electronic Hamiltonian
e
consists of
e
, the kinetic
energy operator for the electrons, V
ne
,the potential energy
of attraction between the electrons and the nuclei, V
ee
,the
inter-electronic repulsions, and V
nn
,the inter-nuclear
repulsions
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Electronic and nuclear motion
The electronic energy or molecular potential energy
E
e
(R
n
) is obtained for various nuclear positions for each
electronic state.
(
n
+ E
e
(R
n
))
n
(R
n
) = E
tot

n
(R
n
)
Here
n
is the kinetic energy operator for the nuclei,

n
(R
n
) is the nuclear wavefunction, and E
tot
is the total
energy which includes the electronic, vibrational and
rotational contributions. The electronic energy then
acts as the potential in which the nuclei move. Here we
concentrate on the electronic part
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Molecular potential energy curve
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Valence Bond Method
Bond regarded as being formed when electron in
an orbital on one atom pairs its spin with that of an
electron in an orbital on another atom.
Consider the approach of two ground state
hydrogen atoms and bond formation in H
2
: Let |
a
and |
b
stand for the 1s orbitals centered on nucleus
a and nucleus b respectively
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Valence Bond wavefunction
Approximate Valence Bond wavefunction:
(1,2) = N{|
a
(1)|
b
(2) + |
b
(1)|
a
(2)} {o(1)|(2) |(1)o(2)}
Overlapping of the orbitals that gives rise to a bond is
accompanied by spin pairing of the electrons.
This wavefunction has cylindrical symmetry about the
inter-nuclear axis, and is said to represent a o-bond
N is a normalization constant
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Electron density along axis
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Electron density along molecular axis according to
simple valence bond wavefunction. Note the pile-up in
the region between the nuclei
N
2
- Valence Bond description
Similar description may be used for diatomics built
from atoms that contribute more than one electron to
bonding: Consider N
2
.
Each atom has three 2p electons available for
bonding.
With the inter-nuclear axis named z-axis, the overlap
of the 2p
z
orbitals and the pairing of those electrons
leads to a o-bond being formed.
The two 2p
x
orbitals overlap in side-wise fashion, and
their electrons pair to form a t-bond.
Likewise, the merging of the two 2p
y
orbitals leads to
another t-bond
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N
2
triple bond (and bonds)
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Polyatomic molecule eg., H
2
O
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Polyatomic molecule: eg. H
2
O: The two unpaired
electrons in O atom can each pair with an electron in an
H 1s orbital, leading to two o bonds. The molecule is
predicted to be bent, at an angle of 90
Bond angles - Hybridization
Poor prediction of bond angles.
Number of bonds that an atom may participate in, for
example the tetravalency of C.
Accounted for by hybridization.
Consider first the example of methane, with four
equivalent C-H bonds.
Ground state: 1s
2
2s
2
2p
x
1
2p
y
1
Promote one electron to get 1s
2
2s
1
2p
x
1
2p
y
1
2p
z
1
Quantum mechanics permits the same electron
distribution to be described in different ways. Construct
a set of four equivalent linear combinations, ie., form
hybrid orbitals
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Methane sp
3
hybrids
b
1
= s + p
x
+ p
y
+ p
z
, b
2
= s p
x
p
y
+ p
z,
b
3
= s p
x
+ p
y

p
z
, and b
4
= s + p
x
p
y
p
z
are four equivalent hybrid
orbitals. The squares of the coefficients give the relative
proportions of the different orbitals in the hybrid
Electron in each of these sp
3
hybrid orbitals pairs up with
electron in H 1s orbital forming o bonds, all four of which
are identical
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Ethene sp
2
hybrids
Now consider ethene, H
2
C=CH
2
, with bond angles close
to 120.
Form sp
2
hybrids using the s and two p orbitals.
b
1
= s + 2
1/2
p
x
b
2
= s + (3/2)
1/2
p
x
(1/2)
1/2
p
y
b
3
= s (3/2)
1/2
p
x
(1/2)
1/2
p
y
These lie in a plane and point towards the corners of an
equilateral triangle. Use these to form o bonds with H
atoms or the other C atom.
Use the remaining unhybridized 2p orbitals on the two
C atoms to form a t bond
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Bonding in ethene
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Ethyne sp hybrid orbitals
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b
1
= s + p
z
b
2
= s p
z
Intermediate hybrid orbitals
Resonance
What about HF?

c
(1,2) = {|
a
(1)|
b
(2) + |
b
(1)|
a
(2)} {o(1)|(2) |(1)o(2)}
with |
a
and |
b
being the 2s of H and the 2p
z
of F, say. But
HF is polar. So expect

i
(1,2) = |
b
(1)|
b
(2) {o(1)|(2) |(1)o(2)} also to be
reasonable
Write =
c
+
i
(trial wave function), and vary the
parameter to minimize the energy, an example of the
Variation theorem. (No approximate wavefunction can
yield an energy that is lower than the exact energy of
the ground state)
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Nature of the resonance hybrid structure
Molecular Orbital Theory
Follow approach similar to what was done for atoms.
Simplest one electron molecular species H
2
+
=
e
e
2
/4
0
r
a
- e
2
/4
0
r
b
+ e
2
/4
0
R
Can treat exactly within Born Oppenheimer, but more
useful to develop approximate description
Write = c
a

a
+ c
b

b
where
a
and
b
are the 1s
orbitals centered on nuclei a and b respectively, vary c
a
and c
b
is a molecular orbital formed by a linear combination
of atomic orbitals (LCAO MO)
From symmetry, expect combination
1
= N
1
(
a
+
b
)
Obtain a second linear combination
2
= N
2
(
a
-
b
)
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H
2
+
Simple LCAO MOs
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MOs characterized by
Energy - Bonding / Antibonding character(*)
Component of electronic angular momentum along axis- 0 (o),
(t), 2 (o) number of nodal planes containing axis.
Transformation under inversion symmetric (g), antisymmetric
(u). (homonuclear)