4.

1 Carter
How do you determine
4.1 Determine the sets of specific atomic orbitals that point group Symmetry?
can be combined to form hybrid orbitals with the
following geometries: (a) trigonal planar, (b) square
planar,(c) trigonal bipyramidal,(d) octahedral
B
Group table are attached.
A
B B
trigonal planar
What are the point groups?

(a) D3h

4.1a-- Determine the sets of specific atomic orbitals that can be combined
to form hybrid orbitals B
(a) trigonal planar -- D3h A
Hybrid orbital construction, Carter, page 100 B B
(x axis coincident with C'2 axis) trigonal planar

“To construct the reducible representation for any set of hybrid

orbitals, count the number of vectors in the basis set that remain
nonshifted by a respresentative operation of each class in the point
group of the system. The number of unshifted vectors is the
character for the class in each case”

What is the reducible representation for the hybrid orbital vectors?

Count # unshifted vectors

t 3 0 1 3 0 1
A’

t = 1 + E’
Which orbitals? A1': s, dz2 E': (px, py) , (dxy, dx2-y2)
 B 4.1b --Determine the sets of specific atomic orbitals that can be
4.1a combined to form hybrid orbitals for a square planar geometry-- XeF4
A
(a) trigonal planar -- D3h B B
trigonal planar
A1': s, dz2 E': (px, py), (dxy, dx2-y2)

What are the hybrid orbitals?

Use 3 atomic orbitals to make 3 hybrid orbitals  can have

A1' E' Notation

What is the point group?
s (px, py) sp2

s (dxy, dx2-y2) sd2 D4h

dz2 (px, py) p2d
dp2

dz2 (dxy, dx2-y2) d3 What is the reducible representation for the hybrid orbital vectors?

4.1b What is the reducible representation for the hybrid orbital vectors
for a square planar geometry-- XeF4?
What are the irreducible representations??
By inspection or……
D4h USE 1
(x axis ni =
gc i r
coincident
with C'2 axis) h c
ni = number of times irreducible representation i occurs in the reducible
representation

h = order of the group = number of elements in the group

c = class of operations

gc = number of operations in the class

i = character of the irreducible representation for the operations of the

Reducible representation
t 4 0 0 2 0 0 0 4 2 0 class

r = character for the reducible representation for the operations of the
What are the irreducible representations??
class
 4.1b Irreducible representations for square planar hybrids 4.1b -- Which orbitals can be used?

t = A1g + B1g + Eu

t 4 0 0 2 0 0 0 4 2 0  /16
4 0 0 4 0 0 0 4 4 0 16 1
4 0 0 -4 0 0 0 4 -4 0 0 0
4 0 0 4 0 0 0 4 4 0 16 1
4 0 0 -4 0 0 0 4 -4 0 0 0
8 0 0 0 0 0 0 -8 0 0 0 0
4 0 0 4 0 0 0 -4 -4 0 0 0
4 0 0 -4 0 0 0 -4 4 0 0 0
4 0 0 4 0 0 0 -4 -4 0 0 0
4 0 0 -4 0 0 0 -4 4 0 0 0
8 0 0 0 0 0 0 8 0 0 16 1 A1g: s , dz2 B1g: dx2-y2 Eu: (px, py)
A1g B1g Eu Notation
s dx2-y2 (px, py) dsp2

t = A1g + B1g + Eu Which orbitals? What are the
hybrid orbitals? dz2 dx2-y2 (px, py) d2p2

4.1c --Determine the sets of specific atomic orbitals that can be

combined to form hybrid orbitals for trigonal bipyramidal
4.1c

-- D3h (a) trigonal bipyramidal -- D3h

(x axis coincident with C'2 axis)

2A1': s, dz2 A2": pz E': (px, py), (dxy, dx2-y2)

What are the hybrid orbitals?

Use 5 atomic orbitals to make 5 hybrid orbitals

2A1' A2" E' Notation

s, dz2 pz (px, py) dsp3

What is the reducible representation for the hybrid orbital vectors?
Count # unshifted vectors s, dz2 pz (dxy, dx2-y2) d3sp
Determine Irreducible reps 2
t 5 1 3 0 3

t = 2A
1 + A2 + E
Which orbitals? A1': s , dz2 A2": pz E':(px, py) ,(dxy, dx2-y2)
4.1d Determine the sets of specific atomic orbitals to form hybrid Which orbitals do we use?
orbitals for octahedral geometry

t = A1g + Eg + T1u

A1g: s Eg: (dz2, dx2-y2) T1u: (px, py, pz)

Determine reducible
representation

t 6 0 0 2 2 0 0 0 4 2
Irreducible rep’s? – A 5 -1 -1 1 1 -1 -1 -1 3 1
1g

t = A1g + Eg + T1u – Eg 3
Only possibility is d2sp3
0 -1 1 -1 -3 -1 0 1 1

4.3 Carter-- Borane MO’s for BH3

Borane, BH3, is an unstable compund produced by thermal
decomposition of H3B•PF3. Although it has not been isolated and
structurally characterized, it probably is trigonal planar. For simple molecule such as MXn, match symmetries of the
atomic orbitals of M with symmetry adapted linear combinations
(SALC’
SALC’s) of atomic orbitals of the X ligands.
ligands.

(a) Develop a general MO scheme for BH3. Assume that only the boron 2s and
2p orbitals interact with the hydrogen 1s orbitals (I.e., the boron 1s orbital is
nonbonding).

(b) The photoelectron spectrum of BH3 has not been observed. Nonetheless, if it
could be taken, what would you expect it to look like, based on your MO mo = a
aAO(M) ± b
bSALC(nX)
nX).
scheme?
SALC(nX)
nX) =
icii where i are atomic orbitals of the X ligands
(c) Compare and contrast the general MO description of BH3 with a valence bond
(VB) model an its related loacalized MO model.
 Molecular Orbital Generation BH3 Molecular Orbitals
What is the symmetry of BH3?
1. Use the directional properties of potentially bonding atomic orbitals on the
outer atoms (depict as vectors) as a basis for a reducible representation of Draw Lewis dot structure…there are 3 boron valence electrons and
the SALC’s in the point group of the molecule. 3 hydrogen valence electrons. The Lewis octet rule cannot be satisfied.
2. Generate the reducible representation characters for these vectors.
+1 if not shifted; -1 if shifted into the negative of itself (head becomes tail);
and 0 if taken into another vector. BH3 3x1 + 3 = 6 valence electrons
3. Decompose the SALC reducible representation into its irreducible
components. # of SALC’s must equal the number of starting basis AO’s
Formal Charge
4. Determine symmetries of potentially bonding AO’s from central atom by H
xo
inspecting the group table unit vector and direct product transformations
listed in the table. B
3 – 3 = 0 for B

xo
ox
5. Central atom AO’s and pendant atom SALC’s of the same symmetry
H H
1–1 = 0 for H
will form both bonding and antibonding LCAO’s (molecular orbitals)

6. Central atom AO’s and pendant atom SALC’s form non-bonding MO’s if no Expect D3h Symmetry -- no lone pair
symmetry match

4.3-- Use the Hybrid orbital approach B General MO scheme

(a) trigonal planar -- D3h A
B B (a) Develop a general MO scheme for BH3. Assume that only the boron
(x axis coincident with C'2 axis) trigonal planar 2s and 2p orbitals interact with the hydrogen 1s orbitals (i.e., the
boron 1s orbital is nonbonding).
Boron Hydrogen atoms

A’1: s E’ : px, py A2: pz
SALC = A’1 + E’

What are the reducible representations for the H(1s) SALC’s?

Count # unshifted vectors

SALC 3 0 1 3 0 1

SALC = - A’1 2 -1 0 2 -1 0
A’ 1+ E’
Which Boron orbitals? A’1: s E’ : px, py A2: pz
1. Bonding MOs always lie lower in energy than the anti-bonding MOs
MO’s for BH3
formed from the same AOs.

2. Nonbonding MOs tend to have energies between those of bonding

and antibonding MOs formed from similar AOs.

3.
interactions tend to have less effective overlap than sigma

pz
interactions.

-bonding MOs tend to have higher energies than -bonding MOs
formed from similar AOs.

* MOs tend to be less anti-bonding and have lower energies than
* MOs formed from similar AOs

4. MO energies tend to rise as the number of nodes increases.

 MOs with no nodes tend to lie lowest, and those with the greatest
number of nodes tend to lie highest in energy.

5. Among s-bonding MOs, those belonging to the totally symmetric

representation tend to lie lowest.

4.3 b The photoelectron spectrum of BH3 has not been observed.

Nonetheless, if it could be taken, what would you expect it to 4.3c Compare and contrast the general MO description of BH3 with a
look like, based on your MO scheme? valence bond (VB) model an its related localized MO model.

Two bands, both with vibrational fine structure. The lower- Similar overall electron distributions.
energy band, from the doubly degenerate
(e') level, should be
roughly twice as big as the higher-energy band, from the VB model ------ sp2 hybridized boron AOs forming 2c-2e
nondegenerate
(a1') level. bonds with hydrogen 1s orbitals.

Localized MO description----- all three bonding pairs in

localized sigma-bonding MO’s.

VB suggestion of energetic equivalence of all three

pairs disagrees with the symmetry restrictions of the
MO’s.
 Octahedral Coordination- Transition Metals What about
bonding?
Only difference is when we derive the reducible representation, have to
include x and y vectors that are perpendicular to the
bond vector.

Example: CO2 Carter, Page 119

Vector basis for a representation of oxygen SALCs of CO2

Filled ligand Empty ligand

p orbitals p orbitals

Use Descent in Symmetry (subgroup) approach ---Carter page 73

Octahedral ML6 molecular orbitals

where L is an arbitrary
donor ligand

Projection Operator Molecular Orbital Orthonormal Properties

How do we determine the SALC combinations in practice? Orthogonality for wave functions that are solutions to the wave equation
SALC(nX)
nX) =
icii where i are atomic orbitals of the X ligands i.e. can be defined by symmetry

ijd =  ij
ij = 1 i=j

Use Projection operator:
ij = 0 ij

Slater overlap integral for Sij =
 A  Bd

wave functions on two atoms
A and B
To get SALC’s for the H atoms---Apply Projection Operator Projection Operator for BH3 Hc
Hc Do same for E’ irreducible representation B
Hb Ha
B
D3h E C13(z) C23(z) C2a C2b C2c
h(xy) S1 3 S2
va
vb
vc
= Hb Ha 3

R j

a
b
c
a
c
b
a
b
c
a
c
b
a
Apply symmetry operations on all orbitals. If class, include all operations
E’ +2 -1 -1 0 0 0 2 -1 -1 0 0 0
in class. “Expanded” table may be useful. For our problem....

D3h E C13(z) C23(z) C2a C2b C2c
h(xy) S1 3 S2
va
vb
vc Get 4
a - 2
b - 2
c Normalization gives:
3 1
R j

a
b
c
a
c
b
a
b
c
a
c
b
 2 (E) =
6
(2 a
 b
 c )
a
See page 143 Carter --- need to get other MO for this irreducible
A’1 +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 representation.
This function must be orthogonal to
1(A1) and
2 (E)
Multiply, add, and normalize to get hydrogen A1 SALC 1
1(A1) =
1
(
a +
b +
c ) Result: ( )
3 E =
2
(
b
c )
3

6.1 Carter Determine the number of frequencies, their symmetries , and the infrared
Midterm Monday, November 7 and Raman activities of the normal modes for the following molecules. Indicate the
number of polarized Raman bands and the number of frequencies that should be
coincident between the two spectra. Representations of the normal modes for these
Class Notes structures can be found in Appendix C. (a) NH3 (b) FeCl63– (c) H2CO (d) PF5 (e)
C2H6 (staggered configuration), (f) H2O2
Homework

Carter, Chapter 3, pages 66-73 Note: Systematic Reduction of Derive the reducible representation for all 3N degrees of freedom of the molecule.
Reducible Representations!!
Carter, Chapter 4 (Symmetry and Chemical Bonding)
Carter Chapter 6 (Vibrational Spectroscopy) Then, categorize symmetries of all of the 3n degrees of freedom by point
group irreducible representations……
Huheey Chapter 3, pp 71-74
Huheey Chapter 5 (Bonding Models in Inorganic Chemistry: The
Covalent Bond)
Huheey Chapter 6, pages 203-218 (The Structure of Molecules)
 Can simplify this greatly! (Carter, page 174) Atomic contributions, by symmetry operation, to the reducible
The character,
I, that contributes to the reducible representation representation for the 3N degrees of freedom for a molecule
for a given operation is universal for all point groups.
Contribution

I = character of the 3 x 3 block matrix of which the operation is Operation per atoma, I
composed
Thus, to find
R, the character for the overall operation, count E 3
the number of atoms that remain nonshifted by the operation , C2 -1
No , and multiply by the contribution per unshifted atom,
i C3 0
C4 1

R = Ni
i C6 2 a Cn = 1 +2cos(2

+2cos(2
/n)
The contribution per nonshifted atom for a particular operation is
1
the same regardless of the orientation of its associated symmetry i -3 Sn = -1 + 2cos(2

2cos(2
/n)
element. S3 -2
S4 -1
Moreover, the value of the contribution per nonshifted atom for S6 0 Where do these come from?
a particular operation is the same in any point group in which
the operation is found.

6.1 a NH3
C3v 6.1 Carter Determine the number of frequencies, their symmetries , and the infrared

R = Ni
i and Raman activities of the normal modes for the following molecules. Indicate the
Determine reducible representations for 3N = 12 degrees of freedom for NH3 number of polarized Raman bands and the number of frequencies that should be
coincident between the two spectra. (a) NH3
all atoms unchanged
1 + 1 + 1+ 1 = +4 Ni
-(
trans+
rot) 6 0 2
From the group table below,
trans = A1 + E

1 atom unchanged
rot = A2 + E The remaining irreducible

+1 rep’s can be obtained from
this reducible rep by using
so that
trans+
rot = 6 0 0 1
ni =
gc i r
h c
2 atoms unshifted
to give
3n-6 = 2A1 + 2E
+2
C3v E 2C3 (z) 3v
4 1 2 A1 +1 +1 +1 z x2+y2, z2
A2 +1 +1 -1 Rz y(3x2-y2)
3 0 1 E +2 -1 0 (x, y) (Rx, Ry) (x2-y2, xy)
(xz, yz)
12 0 2

3n = 3A1 + A2 + 4E pp 183-184
6.1 Carter Determine the number of frequencies, their symmetries , and the
Ammonia -- C3v
trans = A1 + E Carter
infrared and Raman activities of the normal modes for the following molecules.
Summary:
= A2 + E
rot Indicate the number of polarized Raman bands and the number of frequencies
How many independent

3n-6 = 2A1 + 2E that should be coincident between the two spectra. (a) NH3 (b) FeCl63– (c)
Raman and IR frequencies is
H2CO (d) PF5 (e) C2H6 (staggered configuration), (f) H2O2
this?
4

4 (2A1+2E)

R = Ni
i
4 (2A1+2E)
# totally symmetric normal
2(2A1) modes of
3n-6
mode active in both Raman and IR
4 (2A1+2E)
(Carter, page 183)--exclusion rule?
0 normal modes (irreducible rep of 7 1 1 3 3 1 1 1 5 3

3n-6) without x,y,z or quadratic
symmetry? 3 0 -1 1 -1 -3 -1 0 1 1
C3v E 2C3 (z) 3v 21 0 -1 3 -3 -3 -1 0 5 3
A1 +1 +1 +1 z x2+y2, z2
A2 +1 +1 -1 Rz y(3x2-y2)
E +2 -1 0 (x, y) (Rx, Ry) (x2-y2, xy)
(xz, yz)

tot 4 1 2

Atomic contributions, by symmetry operation, to the reducible What are the irreducible representations??
representation for the 3N degrees of freedom for a molecule By inspection or……

Contribution
USE 1
Operation per atoma, I ni =
gc i r
h c
E 3
C2 -1 ni = number of times irreducible representation i occurs in the reducible
C3 0 representation
C4 1 h = order of the group = number of elements in the group
C6 2 a Cn = 1 +2cos(2

+2cos(2
/n)

1 c = class of operations
i -3 Sn = -1 + 2cos(2

2cos(2
/n) gc = number of operations in the class
S3 -2
S4 -1
i = character of the irreducible representation for the operations of the
class
S6 0
Where do these come from?
r = character for the reducible representation for the operations of the
class
 1

trans = T1u ni =
gc i r 2(2T1u)
h c

rot = T1g 3(A1g+Eg+T2g)

3n = A1g + Eg + T1g + T2g + 3T1u + T2u 1(A1g)

3n-6 = A1g + Eg + T2g + 2T1u + T2u 0
1(T2u)