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Fg+
Fu+
a1
b2
Walsh Diagram
The Walsh diagram shows the correlation of the MOs as the
HAH angle changes from 90o to 180o (z axis in the linear
molecule becomes the y axis in the bent molecule)
pHAH 180o:
Note that the non-bonding
1Fg MO is not shown, very
much like the 1s AO of the
A atom
pHAH 90o:
Note that the non-bonding
1a1 MO is not shown, very
much like the 1s AO of the
A atom
Configuration
State
pHAH
LiH2
X 2%u
180o (?)
A 2A1
X 1%g
180o (?)
1
a 3B2, A B2
X 2A1
131o
2
A u
180o
a 1A1
102.4o
3
1
X B1, b B1
134o, 140o
2
X B1
103.4o (110.5o)
2
A A1
144o (180.0o)
1
X A1
104.5o
BeH2
BH2
CH2
NH2(H2O+)
H2O
(all bond angles are determined from electronic spectra, except LiH2 and BeH2, which are unknown species)
BAB Molecules
The symmetric non-hydride molecules BAB are common
molecular species which can also be rationalized with a Walsh
diagram, and a Walsh diagram can be constructed using the
same principles asfor AH2.
Formaldehyde
Formaldehyde has 16 e-. 12 e- are involved in the following
MOs: 3 F bonding, 3 F* anti-bonding, 1 B bonding, 1 B* antibonding and 2 lone pair (oxygen).
The MO diagram for formaldehyde can be constructed by
assigning symmetry species to all of the AOs used to construct
the MOs:
C2v
C2
(xz)
(yz)
2H (1s)
a1 + b1
C (2s)
a1
C (2px)
-1
-1
b1
C (2py)
-1
-1
b2
C (2pz)
a1
O (2s)
a1
O (2px)
-1
-1
b1
O (2py)
-1
-1
b2
O (2pz)
a1
Formaldehyde, 2
+
C
1b1(B)
bonding
O
_
2b2(n)
non-bonding
H
H
+
C
_
O
+
2b1(B*)
anti-bonding
Formaldehyde, 3
6 outer valence e- are involved in major electronic transitions:
Ground: (5a1)2(1b1)2(2b2)2 (X1A1 state)
First excited state: (5a1)2(1b1)2(2b2)1(2b1)1
(gives rise to a3A2 and A1A2 states)
HOMO-LUMO transition involves transfer of in-plane, nonbonding O2py (2b2) e- to the anti-bonding C-O B* (2b1) MO.
This B*7n transition occurs for =C=O, =C=S, -N=O, -NO2 and
-O-N=O chromophores.
The A1A2-X1A1 transition is electric-dipole forbidden, but is
one of the most famous electronic spectra (3530 - 2300 ). It
shows up because of vibronic coupling with the L4 out-ofplane bend (b1) (since A2qB1 = B2, the A1A2-X1A1 borrows
some intensity from the B1B2-X1A1 transition near 1750 .
Formaldehyde, 4
Not only is formaldehyde a prototype for electronic spectroscopy
for heteronuclear chromophores, it was also the first electronic
transition studied with fine rotational detail describing an
asymmetric top.1
Formaldehyde, 5
The a and A states of formaldehyde and other similar
molecules are known as nB* states, and the a - X and A - X
transitions such as that described above are known more
commonly as B*-n or n-to-B* transitions.
The B*-n transitions are easily distinguished from the more
common B*-B transitions (which occur in many aromatic
systems), since the former are blue shifted in a hydrogen
bonding solvent. This is due to interaction of 1s AO of OH
groups (e.g., ethanol) with the n orbital, which increases the
energy of the B*-n transition.
The e- in the 2b1 B* MO energetically favour a pyramidal
shape for the CH2O molecule, because the B* MO can overlap
with 1s + 1s AOs on the H atoms and the 2s AO on the C
atom, resulting in an increase in s character in this MO and a
lowering of energy relative to the planar molecule (two
equivalent schema shown below):
+
H
H
The bend of the C-H bond away from a the usual plane of the
CH2O molecule is 38o in the A1A2 state and 43o in the a3A2
state. Note the MOs must be reclassified in terms of the Cs
point group for these excited states.
Formaldehyde, 6
A Walsh-type diagram can be constructed for formaldehyde,
which correlates the MOs of the planar C2v ground state and
the Cs first excited state:
/0
00
00
00 ' 0
00
00
00
00
Hckel Method
1. Only B electrons are considered, e- in F MOs are neglected.
The B and F MOs in highly symmetric molecules do not
have the proper symmetry for overlap, so in this case this is
not even an approximation. In less symmetric molecules,
the energies of the F MOs are much less than the B MOs
(and F* MOs greater than the B* MOs), so that F MOs can
still be neglected.
2. For m n:
Smn
' 0
Benzene
The Hckel treatment of benzenes 6 2pz AOs give a secular
determinant:
/0
00
00
00
00
00
00
00
00
00
00
0
x 1 0 0 0 1
1 x 1 0 0 0
0 1 x 1 0 0
0 0 1 x 1 0
0 0 0 1 x 1
1 0 0 0 1 x
/0
00
00
00
00
00 ' 0
00
00
00
00
00
0
where:
"& E
$
' x
"+$
" + 2$
Benzene, 2
The symmetry species of the D6h
point group can be assigned to the
MOs (only parts above the rings
are shown, parts below are
identical, but of opposite parity)
The energy of the MOs increases
with the increasing number of
nodal planes perpendicular to the
ring. MOs are antisymmetric w.r.t.
reflection through the ring plane,
just like the p AOs from which
they are constructed.
The ground configuration is:
...(1a2u)2 (1e1g)4, and is a totally
symmetric singlet state: X1A1g
If an e- is promoted from e1g MO to a e2u MO, then the first
excited configuration is ...(1a2u)2 (1e1g)3 (1e2u)1, Since a single
vacancy in 1e1g can be treated like an electron, this
configuration has the same states as the configuration arising
from ...(1a2u)2 (1e1g)1 (1e2u)1.
Thus, the symmetry species of the orbital part of the electronic
wavefunction is obtained from
o
'(Re ) ' e1g e2u ' B1u % B2u % E1u
In the partially occupied MOs, e- may be parallel (S = 1) or
antiparallel (S = 0), meaning there are six possible states:
1,3
B1u, 1,3B2u, 1,3E1u.
CN
CO
CN
NC
Fe
Ni
CN
NC
CN
octahedral
OC
Cl
Cl
CO
CO
tetrahedral
2-
Cu
Cl
Cl
square planar
dz 2
dx 2 & y 2
dxy
dyz
Oh
eg
t 2g
Td
t2
dxz
D3h
a1
D4h
a1g
D4h
g+
C2v
a1
a1
a2
C3v
a1
a1
a2
C4v
a1
b1
b2
D2d
a1
b1
b2
D4h
a1
eN
b1g
eO
b2g
eg
e2
g
b2
b1
e3
eg
(3/5))0
d
E
(2/5))0
t2g
The value of )0 normally corresponds to absorption in the
visible (and sometimes UV) portion of the spectrum,
accounting for the beautiful colourations of transition metal
complexes ()0 is also known as 10Dq, or )T for tetrahedral
complexes, ) for misc. symmetry, etc.).
(a)
(b)
Electronic Transitions
A d6 T.M. complex might have an MO diagram like this:
)(
))
Re Re dJe
Selection Rules, 2
For an allowed transition, *Re* 0, and the symmetry
requirement for this is:
)
))
))
Re,x '
)(
))
Re x Re dJe
Re,y '
)(
))
Re y Re dJe
Re,z '
)(
))
Re z Re dJe
and since
|R e| ' (Re,x)2 % (Re,y)2 % (Re,z)2
))
))
))
))
Selection Rules, 3
If the lower state of the transition is the ground state of a
molecule with all of its MOs filled (no unpaired e-: a closedshell molecule), then the ground electronic state is totally
symmetric and the selection rule simplifies to:
)
))
))
and since:
then:
)
))
))
'(Rv) '(Rv ) '(Re) '(Re ) ' '(T x) and/or '(T y) and/or '(T z)
Summary of Chromophores
The absorption of a photon which causes an electronic
transition can often be traced to specific electrons in the
molecule. For example, if there is a C=O group in the
molecule, an absorption around 290 nm will be observed
(though the precise location will depend on the nature of the
molecule). Functional groups that have characteristic optical
absroptions are called chromophores, their presence often
accounts for the colouration of substances.
All of the examples in this summary are different types of
chromophores.
Group
/cm&1
max/nm
C=O (*-)
61,000
163
15,000
57,300
174
5,500
C=O (*-n)
37,000-35,000
270-290
10-20
H2O (*-n)
60,000
167
7,000
Summary of Chromophores, 2
(2) vibronic transitions
Major problem with interpretation of visible spectra of
octahedral complexes is that d-d transitions are forbidden.
The Laporte selection rule says that the only allowed
transitions are those accompanied by a change in parity (u : g
and g : u only allowed).
The d-d transition is parity forbidden b/c it
corresponds to a g-g transition -but
vibration of the molecule can destroy the
inversion symmetry of the molecule, and
then the g, u classification no longer
applies. Removal of the centre of
symmetry gives rise to a vibronically
allowed transition (though it is weakly
allowed).
(3) charge-transfer transitions
Absorption of radiation may occur as the result of transfer of
an electron from a ligand MO into the d orbitals of the metal
atom, or vice versa. Such transitions are associated with the emoving over large distances, meaning the transition moment
dipoles are very large and absorptions very intense. For
example, in MnO4- ions, the intense violet colour results from
an electron transfer from an MO largely confined on O to an
MO confined on Mn - this is a ligand-metal charge transfer
(LMCT) transition. The reverse, a metal-ligand charge
transfer (MLCT) transition, is also possible (e.g., e- from d
orbitals into B* MOs of aromatic ligands is a very common
example).
Summary of Chromophores, 3
(4) B*-B and B*-n transitions
B*-B transitions
Absorption by a C=C double bond excites the B
e- into an anti-bonding B* orbital, and the
chromophore activity is therefore due to a B*-B
transition. For unconjugated double bonds,
absorption occurs around 180 nm (UV), or 7 eV
for the transition to occur.
When the C=C bond is in a conjugated chain,
the energies of the MOs are closer together, and
the B*-B transition absorbs at longer
wavelengths (can even move to visible region
for really long conjugated chains).
B*-n transitions
Key Concepts
1.
2.
3.
4.
5.
6.