ABCD Questions With Answers

Goals for today:
1) Discuss syllabus
Welcome to Chemistry 120A:

Inorganic Chemistry I
Fall 2016
3:30 4:50 Tues-Thurs
Prof. Jeffrey Rinehart
1) Review the Lewis Dot

structure model
2) Extend the Lewis model
to include resonance and
shape (VSEPR)
3) Book Chapter 3.1 3.3
1
Now you try one

Draw the Lewis structure of HCN
Step 1: Determine the total number of valence electrons.
Step 2: Write the skeleton structure of the molecule.
Step 3: Use two valence electrons to form each bond in the
skeleton structure.
Step 4: Try to satisfy the octets of the atoms by distributing
the remaining valence electrons as nonbonding
electrons.
Step 5: Minimize formal charges (VE unshared bonds)

HCN
HCN
HCN
If you finish early:
HCN

Can you draw a Lewis structure of HNC? Do you think it would be more or less
stable than HCN?
Draw the Lewis structure for CN (not CN). Draw a Lewis structure showing how
2
two CN molecules could react to form a more stable molecule.
A question Lewis dot structures alone cant (completely) answer

FC: 0

SCN
FC: 1 0 0
FC: 1+ 0 2
SCN

SCN

Which structure is least correct?
Deciding between the final two structures depends on which atom can better
stabilize the extra negative charge
3
So back to the original question

FC: 0

SCN
FC: 1 0 0
FC: 1+ 0 2
SCN

SCN

Which structure is most correct?
The answer depends on which atom can better stabilize the extra negative charge
VSEPR model + electronegativity allows the

determination of net dipole moments
Bond polarity:
A difference in the sharing of electrons by a pair of atoms. The more electronegative

atom pulls electrons toward it to create an electric dipole with the negative end closer
to the more electronegative atom. This will still occur even if all formal charges are zero!
Which has the smallest net dipole?

(A)
H2O
H-O-H
(B)
NF3
(C)
NH3
H-N-H
FNF
Bond polarity and the VSEPR model

Which has the largest net dipole?
All are
equivalent
(A)
(B)
(C)
(D)
Although bonds may be polar in a molecule, the dipole moments associated with
the polar bonds may cancel, leading to a non-polar molecule with polar bonds.
6
Bond polarity and the VSEPR model
If all atoms are the same, which VSEPR structure type will have a dipole moment?
(A)
(B)
(C)
(D)
Goals for today:

1) Finish our discussion of
VSEPR theory.
2) Atomic orbitals
3) Periodic trends
Fall 2016
Text: 2.2.2, 2.2.3

Useful online resource:
http://winter.group.shef.ac.u
k/orbitron/
8
Quantum numbers determine the identity of an atomic orbital
What are the quantum numbers

of an electron in a 3dz2 orbital?
a)
b)
c)
d)
n = 3 = 2 m = 0 s=
n = 3 = 2 m = 0 s= -
n = 3 = 0 m = 0 s=
a or b
Radial Component of Wavefunctions (Rn ):

Size or Distance of Orbital from Nucleus
Radial Nodes: When the value of Rn passes through zero and changes sign
Number of radial nodes = n 1
Where is the highest probability location of
an electron in 1s and 2s orbitals?
Remember: probability is proportional to Rn (r)2
a) At the first radial node

b) The most probable location depends on
the number of nodes
c) The most probable location is on the
nucleus
d) Quantum mechanics is a lie!
Radial wavefunction
Rn (r)
cross section view
10
Radial Probability Functions (r2R2)

Probability of finding an electron in an orbital in a certain
region of space
What orbital does this radial function

describe?
a)
b)
c)
d)
3s
3p
3d
Cannot be any of these
11
Name this orbital!

Remember, # of radial nodes = n - - 1
Remember, # of angular nodes determines (0 = s, 1 = p, 2 = d)
a) 4dxy
b) 4dx2-y2
c) 3dx2-y2
d) 5dxy
12
Goals for today:

2) Multielectron systems
3) Periodic trends
Fall 2016
4) Interacting atomic
orbitals to form molecular
orbitals
Text: 2.2, 2.3, 5.1
13
Name this other orbital!

Remember, # of angular nodes determines (0 = s, 1 = p, 2 = d)
Remember, # of radial nodes = n - - 1
a) 5s
b) 3dz2
c) 2s
d) 3s
outside view
Angular nodes = 0 ( = 0) s orbital

Radial nodes = 2 (n - - 1 = 2) n = 3
sliced view
14
r22
r22
r22
The following three radial distribution functions

could represent what series of orbitals?
r22
(all three)
r
A 4s, 3s, 2s
B 3s, 3p, 3d
C 4s, 4p, 4d
D 3dxz, 3dyz 3dz2
15
Voting Card Question
Electrons in which orbital are shielded to the greatest extent?

A 2s
B 3s
C 3px
D 3dz2
16
Which has the largest radius?

A Na+
B K+
C Cl
D I
17

A (g)
A (g) + e
E = Electron Affinity (EA)
Which is the least likely to give up an electron?

A N
B F
C Ne
D Na
18
Bond order =
# of bonding electrons - # of antibonding electrons

2
Energy
?
He(2s )
1*
1sA
What is the bond order of He2?
a) 1
b) 2
c) -1
d) 0
?
1sB
?
1
He(2sB)
Goals for today:
Spring 2015
1) Construct simple molecular

orbitals and molecular
orbital diagrams for
diatomic main group
molecules.
Reading: 5.1 5.2
Deciding gerade vs. ungerade vs. neither

a) gerade
b) ungerade
c) neither
a) gerade
b) ungerade
c) neither
a) gerade
b) ungerade
c) neither
a) gerade
b) ungerade
c) neither
a) gerade
b) ungerade
c) neither
21
Molecular orbitals from atomic pz orbitals

new node!
(pz + pz)
(pz pz)
Which of these combinations is antibonding?
a) pz + pz
c) both
b) pz pz
d)
neither
22
Orbitals with the same energy are degenerate

y
#2 (py py)
#1 (py + py)
y
#4 (px px)
#3 (px + px)
Which orbital pairs are degenerate with each other?
A) #1/#2 and #3/#4

C) None
B) Only #1/#3
D) #1/#3 and #2/#4
23
Constructing a molecular orbital diagram for all

atomic p orbitals
pz + pz
pz px py
pz px py
atom a
atom b
pz pz
Which orbital interaction creates the most bonding and most antibonding combination?
a) px and px
b) py and py
c) pz and pz
d) px and py
24
Constructing a molecular orbital diagram for all

atomic p orbitals
1u*
pz px py
atom a
1u
1g
What should the unlabeled set of degenerate orbitals be labeled?
a) 2u*
b) 1u*
c) 1g*
d) 1u
pz px py
atom b
(py py)
(px px)
25
Example: O2
2*
1g*
2pz 2px 2py
2pz 2px 2py

1u
2
1*
2s
2s
O
1
How many electrons does each EACH oxygen provide to this MO diagram?
a) 5
c) 6
b) 4
d) 8
26
Example: O2
2*
1g*
pz px py
pz px py
1u
2
1*
s
s
O
1
What is the highest occupied molecular orbital (HOMO) for O2?
a) 2
c) 1g*
b) 1u
d) 2*
27
Example: O2
2*
1g*
pz px py
pz px py
1u
2
1*
s
s
O
What is the bond order of O2?

a) 3
c) 2
O
1
b) 1
d) 4
28
Goals for today:
1) Review the cause and

effects of s-p mixing
Spring 2015
2) Translate our knowledge of

homonuclear diatomics
(two of the same atom e.g.
O2) to heteronuclear
diatomics (two different
metals e.g. CO)
5.2.2-5.2.4, 5.3
Carbon monoxide MO diagram

0
How many bonds does carbon

monoxide have?
2*
5
10
E
1*
2
2p
15
20
2p
1
2s
a) 1
b) 2
c) 3
d) 0
1*
25
30
35
2s
1
C
30
Carbon monoxide MO diagram

Which atom has a larger portion of the
LUMO orbital on it?
0
2*
a) carbon
b) oxygen
c) too complicated
d) equal
5
10
E
1*
2
2p
15
20
2p
1
2s
1*
25
30
35
2s
1
C
31
A more complex heteronuclear orbital interaction: BF

0
Which fluorine orbital
will the boron 2s orbital
form the strongest
bond with?
5
2p
10
E
15
2s
20
2p
25
30
35
40
45
boron
2s
fluorine
a) 2s
b) 2px
c) 2pz
d) no interaction

2*
0
5
2p
1*
2s
2
1
10
E
15
20
1*
Shown are two occupied orbitals

from the diagram for BF. What is
their symmetry label?
2p
25
30
35
40
45
boron
2s
fluorine
a) 1
b) 2
c) 1*
d) 1

2*
0
5
2p
1*
2s
2
1
Where is the F located in the 1

orbital depicted below?
10
E
15
20
1*
2p
25
30
35
40
45
boron
2s
fluorine
Goals for today:

1) Simple introduction to
computational methods in
chemistry / WebMO
2) Recognize and label all
symmetry elements
3) Symmetry resources:
Spring 2015
http://symmetry.otterbein.
edu/gallery/index.html
https://www.webmo.net/
Chapter 5 in book

1
4
5
* By definition, rotations
occur in a counterclockwise
fashion
3
If three consecutive C4 operations are performed (denoted C43) on

this molecule, which position will sphere 1 end up in?
A1
B3
C5
D4

C2
C2
C6 and C3
C2
* The largest valued n is

referred to as the primary
or principal rotation axis
C2
C2
C2
How many different types of Cn axes are in a snowflake?

A Only C6
B C4 and C6
C C2 and C6
D C2 C3 and C6
The five symmetry elements : rotation axis

Which of these does not have a rotation axis symmetry element?
38
How many mirror planes

does this object have?
A one
B five
C six
D eight
How many mirror planes

does this object have?
A one
B five
C six
D eight

Is there an Inversion Center?
A Yes
B No
41

A Yes
B - No
42

A Yes
B - No
43

A Yes
B - No
44
What is the order of the improper rotation for sulfur (S8)?

A S8
B S2 = i
C S4
D no Sn
Goals for today:

1) Practice tabulating symmetry
elements
2) Use symmetry to determine
the point group of a molecule
3) Resources:
Spring 2015
http://symmetry.otterbein.
edu/gallery/index.html
https://www.webmo.net/
Chapter 5 in book
How many different symmetry operations are there for BH3?

A 12
B6
C 10
D 14
Top
Side
Step 1: Rotation axes
A) Is there a main rotation axis?

i) be sure to count any dependent axes
e.g. (C41 and C42 = C2 and C43 and C44 = E)
B) Are there axes perpendicular to the main axis?
Step 2: Mirror planes
A) Is there a mirror plane perpendicular to the main rotation axis? h
B) Are there mirror planes parallel to the main rotation axis?

i) through at least one outer atom = v
ii) in between outer atoms = d
Step 3: Inversion symmetry A) Does each atom at (x,y,z) have an equivalent at (-x,-y,-z)?
i) just like with the identity (E), a molecule
can only have one inversion center
Step 4: Improper rotation A) Are there combination rotation/reflections Sn?
i) Remember S1 = and S2 = I
ii) A molecule having both a principle Cn axis and a
h plane will always have an improper axis of order n
47
Determining Molecular
Point Groups
Point-Group Flow Chart
n Cn
EXAMPLE:
A Td
B C3V
C D3h
D D3d
Point Groups
n Cn
EXAMPLE:
A Oh
B C2v
C Cv
D Dh
Point Groups
n Cn
H
EXAMPLE:
H
H
C
H
A Td
B D3d
C C3v
D Oh
Point Groups
n Cn
EXAMPLE:
A D2d
B C2h
C Cs
D C2v
Point Groups
n Cn
EXAMPLE:
A Td
B C3V
C D3h
D D3d
Point Groups
n Cn
EXAMPLE:
A Cs
B Ci
C D2d
D D2h
Point Groups
n Cn
EXAMPLE:
H3N
Cl
Pt
NH3
A Cs
B C4h
Cl
C D4h
D C2v
Point Groups
n Cn
EXAMPLE:
Co
A Cs
B C4v
C D4d
D D4h
Point Groups
n Cn
NH3
EXAMPLE:
H3 N
Mo
H3 N
CO
CO
CO
A D3h
B C3v
C Oh
D C2v
Point Groups
n Cn
CO
EXAMPLE:
H3N
Mo
H3N
NH3
CO
CO
A D3h
B C3v
C Oh
D C2v
Practice for test A = true; B = false

In the homonuclear diatomic molecule N2, the molecular orbital with composition
(2pz 2pz) is higher in energy than the (2pz + 2pz) molecular orbital.
FALSE
According to VSEPR theory, a molecule with steric number of four and two lone pairs FALSE
will be linear.
The orbital angular momentum quantum number (l) for a 3dz2 orbital will be the
same as for a 4dx2y2 orbital.
TRUE
In carbon monoxide (CO), the bonding MO made from 2p orbitals has more electron TRUE
density on the carbon atom.
FALSE
Diatomic O2 and O22 are both paramagnetic.
The radial probability function (~r22) describes the probability of finding an electron at
a given radius, summed over the surface area of the sphere described by that radius. TRUE
MO theory with s-p mixing predicts the paramagnetism (unpaired electron(s)) of B2. TRUE
58
Goals for today:
Fall 2016
1) Learn how to read a

character table to
understand the symmetry
of any point group
2) Read: Chapter 5.4
Transformation properties of an s orbital in C2v

1
So which Mulliken symbol describes the irreducible representation for this orbital?
In the C2v point group, an s-orbital centered at the origin (0,0,0) has a1 symmetry and will
therefore only interact with other orbitals that have a1 symmetry
What about other orbitals?

py orbital in C2v
1
In the C2v point group, an s-orbital centered at the origin (0,0,0) has b2 symmetry and will
therefore only interact with other orbitals that have b2 symmetry
What about other orbitals?

px orbital in C2v
z
?
x
Point Groups
a) D2h
c) Cv
b) C2h
d) Dh
63
Goals for today:

1) Use a character table to
determine the MO Diagram
for H2O.
Fall 2016
2) Use a character table to

determine the MO Diagram
for N2H2.
3) Figure out where characters
come from (Spoiler: they
come from math)
How do we represent the orbitals of the two hydrogen atoms?

SALC: Symmetry Adapted Linear Combination
Making mini-MOs (SALCs) simplifies the construction of the final MO diagram in cases with
more than two atoms.
z
y
2
1
x
What is the reducible representation (G) for 2H in C2v?

a) 2,2,2,2
b) 2,0,0,2
c) 2,0,2,0
d) 2,1,2,1
65
Symmetry Adapted Linear Combinations (SALCs) of 2H in C2v
G
# of irreducible
Representations
of a given type
1
=
h (order)
S
R
0
# operations
In class
Character of
Reducible
representation
Character of
Irreducible
representation
What are the irreducible reps of the 2H atoms in H2O?

a) A1 + A2
b) A1 + B1
c) A1 + B2
d) A2 + B2
66
Symmetry Adapted Linear Combinations (SALCs) of 2H in C2v
G = A1 + B2
z
y
x
a1
b2
Which oxygen orbital will not interact with any SALC?

a) px
b) py
c) pz
d) all
interact
67
Molecular orbital diagram of H2N2

y
H
N
x
z
N
H
Which is not a symmetry element

of H2N2?
a) i
b) C2
c) v
d) h
68
What is the point group of H2N2?

a) D2h
b) C2v
c) Cs or Ci
d) C2h
69
Determine all of the atomic orbitals we need to account for:
On N1 (2s + 2px + 2py + 2

On N2 (2s + 2px + 2py + 2
2s
=?
What is the reducible representation of the 2s orbitals of the N2 SALC in C2h?
2s
a) 2 2 2 2
b) 2 0 2 0
c) 2 0 0 2
d) 2 0 0 2
70
=?
What is the reducible representation of the

2px orbitals of the N2 SALC in C2h?
a) 2 2 2 2 b) 2 0 2 0 c) 2 0 0 2 d) 2 0 0 2
71
=?

2py orbitals of the N2 SALC in C2h?
a) 2 2 2 2 b) 2 0 2 0 c) 2 0 0 2 d) 2 0 0 2
72
=?

2pz orbitals of the N2 SALC in C2h?
a) 2 2 2 2 b) 2 0 2 0 c) 2 0 0 2 d) 2 0 0 2
73
=2 0
0 2
Ag + B u
(2px/2px) = 2 0
0 2
Ag + B u
(2py/2py) = 2 0
0 2
Ag + B u
(2pz/2pz) = 2 0
0 2
Au + B g
(2s/2s)
By inspection, can you determine the irreducible representations of all of the NN SALCs?
a) 3Ag + 3Bu + 1Bg + 1Au b) 4Ag + 4Bu c) 2Ag + 2Bu + 2Bg + 2Au
d) None of these
74
Defining a full character table

C2v
C2
sv(xz)
sv(yz)
A1
x2, y2, z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
We found three of the representations just by seeing how the Cartesian coordinates
transform in space. How do we find the last irreducible representation?
Properties of point groups:
1) The order of a group is equal to the total number of symmetry operations
What is the order of C2v?
a) 2
b) 6
c) 4
d) 3
75

C2v
C2
sv(xz)
sv(yz)
A1
x2, y2, z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz

2) Symmetry operations are grouped by class. Classes are always the same type of
operation and always return the same character for a given irreducible representation
How many classes does C2v have?

a) 2
c) 4
b) 6
d) 3
76

C2v
C2
sv(xz)
sv(yz)
A1
x2, y2, z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
3) # of irreducible representations = # of classes

4) the sum of the squares of the characters under E (dimensions) equals the order
of the group.
What is the dimension of the A2 irreducible

representation?
a) 2
c) 1
b) 0
d) -1
77

C2v
C2
sv(xz)
sv(yz)
A1
x2, y2, z2
A2
-1
-1
Rz
xy
B1
-1
-1
x, Ry
xz
B2
-1
-1
y, Rx
yz
7) All irreducible representations are orthogonal. (i.e. the sum of characters for two
classes multiplied together is zero)
(B1)(A2) = (1)(1)(1) + (-1)(?)(1) + (1)(?)(1) + (-1)(?)(1) = 0

(B2)(A2) = (1)(1)(1) + (-1)(?)(1) + (-1)(?)(1) + (1)(?)(1) = 0
What are the characters of A2?
a) 1, 2, 0, -1 b) 1, -1, 1, -1
c) 1, 1, 1, 1 d) 1, 1, -1, -1
78
Goals for today:
Halloween Edition
Fall 2016
1) Finish determining the MO

Diagram for N2H2.
2) Figure out where characters
come from (Spoiler: they
come from math) (Book 4.3)
Transformation matrix definitions of the operations in C2v

C2
z
y
x
C2 Transformation Matrix
(x,y,z -x, -y, z)
?1 ?0
0 1
? ?
?0 ?0
0 x x
?
0 y = y
?
1
?
z z
sv(xz) Transformation Matrix

(x,y,z x,-y,z)
?1
?0
?0
?0 x x
y = y
?0

?1
z z
s(xz)
z
y
x
?0
? 1
?0
s(yz)
z
1 0 0
0 1 0
y
x
0 0 1
1 0 0
0 1 0
0 0 1
1 0 0
0 1 0
0 0 1
1 0 0
0 1 1
0 1 1
80
Rotation matrix definitions of the operations in C2v

C2
z
y
x
C2 Transformation Matrix
(Rx, Ry, Rz Rx, Ry, Rz)
?1 ?0
0 1
? ?
? ?0
0
sv(xz) Transformation Matrix

(Rx, Ry, Rz Rx, Ry, Rz)
?1
0
?
?0
0 Rx Rx
?
0 Ry = Ry
?
1
?
Rz Rz
s(xz)
z
y
x
0 Rx Rx
?
0 Ry = Ry
?
?0 ?1
Rz Rz
?0
?1
s(yz)
z
1 0 0
y 0 1 0
x
0 0 1
1 0 0
0 1 0
0 0 1
1 0 0
0 1 0
0 0 1
1 0 0
0 1 1
0 1 1
81
How do we assign Mulliken symbols?

1) E : ( = 1) A or B
( = 2)
E
( = 3)
T
4) operation after Cn and all

collinear axes :
( = positive) 1
( = negative) 2
2) Cn : ( = 1) A
( = 1) B
5) h :
3) i : ( = positive) g
( = negative) u
6) Use only what you need
( = positive)
( = negative)
What is the missing Mulliken symbol?

a) Au
b) Bg
c) B1
d) B
82

1) E : ( = 1) A or B
( = 2)
E
( = 3)
T

collinear axes :
( = positive) 1
( = negative) 2
2) Cn : ( = 1) A
( = 1) B
5) h :
( = negative) u
( = positive)
( = negative)

a) A3
b) B1
c) B1
d) A1
83

1) E : ( = 1) A or B
( = 2)
E
( = 3)
T

collinear axes :
( = positive) 1
( = negative) 2
2) Cn : ( = 1) A
( = 1) B
5) h :
( = negative) u
( = positive)
( = negative)

a) B3g
b) E
c) Au
d) Eg
84
Goals for today:
November 1, 2016
Prof. Alina Schimpf
1) Understand how to build

character tables with
degenerate representations
2) Use the projection operator
to draw pictures of
molecular orbitals
What is the transformation matrix for a C32 rotation in C3v?

A
sin 4 / 3 cos 4 / 3 0
cos 4 / 3 sin 4 / 3 0
0
0
1
B
cos 4 / 3 sin 4 / 3 0
sin 4 / 3 cos 4 / 3 0
0
0
1
sin 2 / 3 cos 2 / 3 0
cos 2 / 3 sin 2 / 3 0
0
0
1
1 0 0
0 1 0
0 0 1
86
We just saw that x and y axes cannot be considered separately in C3v
Looking at the character table, which set of orbitals must be

considered together?
A px and pz
B dxz and dxy
C dxz and dyz
D dxz and py
C3v E 2C3 3sv

A1
A2
Rz
z2
0 (x,y), (Rx, Ry) (x2y2, xy), (xz, yz)
87
Goals for today:
November 3, 2016
Prof. Alina Schimpf
1) Construct SALCs from

doubly and triply
degenerate irreducible
representations
2) Use SALCs to predict
what molecular vibrations
look like
Reduction Formula for Irreducible Representations

# of irreducible
Representations
Of a given type
1
order
SR
# operations
In class
Character of
Reducible
representation
Character of
Irreducible
representation
x
C
A
y
C3v
2C3
3sv
1
What is the order of C3v?

a) 2
b) 6
c) 4
d) 3
89
Goals for today:

1) Review determination of
molecular motions from
symmetry considerations (Ch.
4.4)
Fall 2016
2) Using MO theory to understand

and predict reactivity (Ch. 6.4)
3) Extend our understanding of
electronic structure to transition
metals (Ch. 10.1-10.2)
Determining the molecular vibrations of

H2O
Vibrations = 2A1 and B1
Which of these vibrational modes has B1 symmetry?

91
IR active vibrational modes

Step 4: Determine which vibrational modes are IR active
Vibrations = 2A1 and B1
Any vibrational mode that transforms in the same way as x, y, or z will have a net
shift in dipole moment and therefore be IR active
Which of these vibrational modes will show an absorption in the IR region?
2A1 and B1
A1 and B1
B1 and B2
92
Our rules for forming strong interactions still apply:

1) There must be orbital overlap
2) The orbital energies must be close
Which orbital approaching along the z axis in the orientation shown is likely to
interact with the occupied orbital below to form a Lewis acid/base adduct?
occupied
occupied
occupied
y
x
occupied
unoccupied
Various reactions are possible when frontier orbitals

(HOMO & LUMO) interact
The type of reaction is determined by the energy difference between frontier orbitals
If the LUMO of one reactant is significantly lower in energy than the HOMO of
the other reactant, an electron transfer will occur
LUMO (3d)
What is water in this case?
HOMO (4s)
Lewis acid
LUMO
Lewis base
HOMO
Oxidant
H2O
Ca
A&C
Various reactions are possible when frontier orbitals

(HOMO & LUMO) interact
The type of reaction is determined by the energy difference between frontier orbitals
If the LUMO of one reactant is significantly lower in energy than the HOMO of
the other reactant, an electron transfer will occur
LUMO
What is water in this case?
HOMO
Lewis acid
Lewis base
LUMO
HOMO
Electrophile
F2
H2O
A&C
A symmetric ML6 complex
L
L
M
L
L
L
What point group does this

molecule belong to?
a) Ih
b) D4h
c) C4v
d) Oh
96
Crystal field of a square pyramidal complex

L
dx2-y2 dz2
dxz
L
dxy
dyz
L
M
What is the predicted crystal field splitting for a square pyramidal complex?
dxy
d z2
a)
b)
dz2 dx2-y2
dx2-y2 dxy
dxz dyz
c)
dx2-y2
d z2
dxy
dxz dyz
dxz dyz
d)
dx2-y2
dxy
d z2
dyz
dxz
97
Magnetic data can be used to predict geometry

(and vice versa)
dxy
dxz
dx2-y2
dyz
dx2-y2
dx2-y2 dz2
d z2
d z2
dxy
dxy
dxy
dxz
dyz
OCTAHEDRAL
dx2-y2 dz2
TETRAHEDRAL
dyz
dxz
SQUARE
PLANAR
d z2
dyz
dxz
SQUARE
PYRAMIDAL
dxy
dx2-y2
dyz
dxz
TRIGONAL
BIPYRAMIDAL
Magnetic measurements show that an Fe(II)L4 compound is diamagnetic

(no unpaired electrons). What is the geometry of the compound?
a) Tetrahedral
b) Square planar
c) Square Pyramidal
d) trigonal bipyramidal
98
Goals for today:

1) Use crystal field
theory to determine
d-orbital splittings
for high-symmetry
transition metal
coordination
complexes.
Fall 2016
2) Apply symmetry and

molecular orbital
theory to explain the
spectrochemical
series
The spectrochemical series is determined by the type of

coordination bond formed between the metal and ligand
[I] < [Br] < [Cl] < [N3] < [F] < [OH] < H2O
< NH3 py < [CH3] < [H] < [C6H5] < [CN] < CO
Pure donors
NH3
2a1
Metal
Highest Occupied Molecular Orbital (HOMO)

Pure sigma donors have electron density not
involved in bonding that can be used to
stabilize a transition metal complex
How would we classify this type of ligand

using Lewis acid/base terminology?
a) acid
b) base
100
The Spectrochemical Series:

donor ligands
[I] < [Br] < [Cl] < [N3] < [F] < [OH] < H2O
< NH3 py < [CH3] < [H] < [C6H5] < [CN] < CO
Weak field donors
Cl
Metal
Pi donors have electrons in orbitals that can

participate in pi bonding with the metal.
They are called weak-field because they
lead to small orbital splittings

a) acid
b) base
101
The Spectrochemical Series:

acceptors ligands
[I] < [Br] < [Cl] < [N3] < [F] < [OH] < H2O
< NH3 py < [CH3] < [H] < [C6H5] < [CN] < CO
Strong field acceptors
empty *
orbital
Metal
Pi acceptors have empty pi orbitals that are

energetically accessible for interaction with
occupied metal orbitals. They are called strongfield because they lead to large orbital splittings.

a) acid
b) base
To fully understand these interactions, we must now develop full MO diagrams102
Reducible representation of -symmetry SALCs in Oh
What is red for s-orbitals of the ligand atoms (1 6)?
red = 6 0 0 2 2 0 0 0 4 2
red = 6 0 0 2 2 0 0 0 2 2
red = 6 0 0 2 2 0 0 0 2 2
red = 6 0 0 4 4 0 0 0 2 2
103
Irreducible representations of the octahedral -symmetry SALCs
order (h) = 48
red = 6 0 0 2 2 0 0 0 4 2
What irreducible representations are contained in red?
red = a1g + t2g + eg
red = a1g + t2u + eg
red = a1g + t1u + eu
104
Using tricks to determine the shape of octahedral -symmetry SALCs
The a1g SALC has the same symmetry as an s-orbital. What must it look like?

105
Using tricks to determine the shape of octahedral -symmetry SALCs
The t1u SALCs have the same symmetry as the p-orbitals. What must they look like?

106
Determining -symmetry SALC interactions
1 5 2 2 2 2
(dz2) =
4
2
Which d orbitals can interact with our s-orbital SALCs?

a) None
b) All
c) Only dz2 dxz and dyz
d) Only dz2 and dx2y2
107
-symmetry SALCs of a tetrahedral complex
red = 4 1 0 2 2
red = 4 0 2 2 2
red = 4 1 0 0 2
red = 4 1 0 0 4
108
Irreducible representations of the octahedral s-orbital SALC
order (h) = 24
red = 4 1 0 0 2
red = a1 + t1
red = a1 + t2
red = 2e
red = 2a1 + 2a2
109
Goals for today:

1) Derive MOs for
octahedral and
tetrahedral
complexes (10.3)
Fall 2016
2) Use molecular
orbital theory to
explain the
spectrochemical
series
Determining -symmetry SALC interactions
1 5 2 2 2 2
(dz2) =
4
2
Which metal d orbitals can interact with our s-orbital SALCs?
a) None
b) All
c) Only dz2 dxz and dyz
d) Only dz2 and dx2y2
111
-symmetry SALCs of a tetrahedral complex
red = 4 1 0 2 2
red = 4 0 2 2 2
red = 4 1 0 0 2
red = 4 1 0 0 4
112
Irreducible representations of the octahedral s-orbital SALC
order (h) = 24
red = 4 1 0 0 2
red = a1 + t1
red = a1 + t2
red = 2e
red = 2a1 + 2a2
113
Goals for today:

1) Review the electronic
structure factors leading
to high-spin/low-spin
states
2) Determine electronic
configurations that will
lead to Jahn-Teller
distortions
Fall 2016
3) Understand how to use

Tanabe-Sugano diagrams
to determine excited state
properties and
spectroscopic transitions
(Book 10.4.4 - 10.4.5, 10.5,
11.3.3-11.3.5)
Differentiating high-spin from low-spin

1) Check if multiple spin configurations are possible.
In which of these compounds are both high and low
spin ground state configurations possible? (Hint: draw
the crystal field and try adding electrons)
tetrahedral symmetry, two d-electrons (d2)
octahedral symmetry, two d-electrons (d2)
octahedral symmetry, seven d-electrons (d7)
octahedral symmetry, eight d-electrons (d8)
115
Differentiating high-spin from low-spin

1) Check if multiple spin configurations are possible.
2) Is the complex tetrahedral? In 99.9% of cases it is high spin
3) Are the ligands strong or weak field?
Which complex is low spin?
[Co(H2O)6]2+
[CoCl6]4
[Co(CN)6]3
[Cu(CN)6]4
116
The ground state is the lowest energy state therefore

the distortion must lower the total energy
Energy
Use crystal field theory to

identify the highest energy
orbital for the elongation case
eg
t2g
Cu(II) after J-T

compression
Cu(II) Oh
Cu(II) after J-T

elongation
xy
x2-y2
z2
xz
eg
eg
eg
Energy
eg
t2g
t2g
t2g
Which electron configuration will not lead to a J-T distortion?
t2g
Summary of Jahn-Teller distortion rules

Distortions are strong if the involve the eg symmetry orbitals.
Distortions are weak if they involve the t2g symmetry orbitals.
strong Jahn-Teller
(large distortion)
weak Jahn-Teller
(small distortion)
eg
eg
t2g
d electrons
High spin
Low spin
1
weak
2
weak
A
B
t2g
3
strong
?
weak
weak
strong
weak
strong
strong
C
strong
D none
weak
weak
weak
weak
strong
9
strong
Square planar complexes in low-spin d8 metal ions

4d and 5d metal complexes with the d8 configuration are low-spin and square-planar,
while 3d8 complexes are high-spin tetrahedral except with strong-field ligands
I
N
C
R
E
A
S
I
N
G
d8 metal ions:
M(I)
M(II)
Which of these is likely to NOT

be square planar?
M(III)
rare
oxidation
states
[PdCl4]2-
[Ni(H2O)4]2+
[Ni(CN)4]2
[AuCl4]
Naming scheme for describing multi-electron states

The superscript describes
the spin multiplicity (2S+1)
What is the term symbol for

this electronic structure?
6A
The letter describes the

degeneracy (similar to
orbital degeneracy)
The subscript describes the

electronic symmetry
(beyond the scope of this
class)
3E
2E
2T
3T
2T
2
121
The Racah parameter scales inversely with the ionic radius
Racah parameter
(B in cm1)
Mn(II)
Fe(III)
Co(IV)
859
1029
1185
ionic
radius
(pm)
~75
~60
~53
Which will have the largest

Racah parameter?
Pd(II)
Pt(II)
Ni(II)
122
Racah parameters tell us if a complex is likely to be low or high spin

M
Racah parameter
(B in cm1)
Mn(II)
Fe(III)
Co(IV)
859
1029
1185
ionic
radius
(pm)
~75
~60
~53
any
d5 metal
Energy/B
A Mn(II), Fe(III) and Co(IV) complex all have the same ligand field.
Which line on the plot most likely corresponds to the Mn(II) complex?
2T
2
6A
o/B
123
Goals for today:
Fall 2016
1) Understand how to use

Tanabe-Sugano diagrams
to determine excited state
properties and
spectroscopic transitions
2) Color!
(Book 11.3.3-11.3.5)
Determining the free-ion ground state symbol

1) Highest spin state is ground state
(2S+1)L
2) If states have same spin, highest L is ground state
d5
only one way to get this spin (6S)
d3
ground state has 2S+1 = 4

and max L = 3
ml = 2
-1
-2
What is the ground state term symbol for this electronic structure?
U(III): 5f3
ml = 3
-1
-2
-3
A
B
C
D
(4F)
L=0S
L=1P
L=2D
L=3F
L=4G
L=5H
L=6I
2A
4I
2F
4H
125
Intensity of electronic transitions is termined by whether they are

allowed or forbidden
4A
Two important rules
(1) Spin selection rule:

Transitions between different
spin multiplicities are forbidden.
2T2 is spin allowed
4A
2T2 is spin forbidden
E/B
2E
2E
2E
4T
1
g u and u g are Laporte allowed
4T None are
1 allowed!
A
6A
g g and u u are Laporte forbidden
(2) Laporte selection rule:

Transitions between orbitals with
the same symmetry with respect
to inversion are forbidden.
2T
1
C
1
Do/B
6A
2T
2
1
Which of these transitions is

Laporte allowed?
126
Intensity of electronic transitions is termined by whether they are

allowed or forbidden
4A
Two important rules
(1) Spin selection rule:

Transitions between different
spin multiplicities are forbidden.
2T2 is spin allowed
4A
2T2 is spin forbidden
E/B
2E
2E
2E
4T
1
g u and u g are Laporte allowed
4T None are
1 allowed!
A
6A
g g and u u are Laporte forbidden
(2) Laporte selection rule:

Transitions between orbitals with
the same symmetry with respect
to inversion are forbidden.
2T
1
C
1
Do/B
6A
2T
2
1
Which of these transitions is

spin allowed?
127
Using the Tanabe-Sugano diagram: ruby absorption spectrum

d3 Tananbe-Sugano diagram
4A
2A
2
4T
1
4T
1
2A
4 A2
2E
4A2
4T
1
E/B
4T (4F)
1
4T
2
2T
2
2F
2T
1
2E
2G
4P
4A
4F
What would you predict the transition at ~250 nm to be?

A) 2T2 4A2
B) 2A1 4A2
C) 4T1 (2F) 4A2
Do/B
D) 2A2 4A2
128
Goals for today:
Fall 2016
1) Finish our introduction to

understanding color
2) Discuss the simple models
of the electronic structure
of infinite solids
Interpreting the band diagram
more antibonding
Fermi level: highest

occupied orbital level
Energy
unoccupied orbitals
occupied orbitals
What does the band look like at the Fermi level?

more bonding
1s
Band
For each orbital in the smallest

defined unit (unit cell), there is
one band
a)
b)
c)
d)
130
What can we learn from looking at a band diagram?

Which of these has the strongest interaction between orbitals in the band?
(A)
k
E
(C)
k
(B)
k
(D)
k
131

ABCD Questions With Answers

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

ABCD Questions With Answers

Uploaded by

Copyright:

Available Formats

Goals for today:

Welcome to Chemistry 120A:

1) Review the Lewis Dot

Now you try one

If you finish early:

A question Lewis dot structures alone cant (completely) answer

Which structure is least correct?

So back to the original question

Which structure is most correct?

VSEPR model + electronegativity allows the

A difference in the sharing of electrons by a pair of atoms. The more electronegative

Which has the smallest net dipole?

Bond polarity and the VSEPR model

Bond polarity and the VSEPR model

Goals for today:

Text: 2.2.2, 2.2.3

Quantum numbers determine the identity of an atomic orbital

What are the quantum numbers

Radial Component of Wavefunctions (Rn ):

a) At the first radial node

cross section view

Radial Probability Functions (r2R2)

What orbital does this radial function

Name this orbital!

Goals for today:

Name this other orbital!

Angular nodes = 0 ( = 0) s orbital

The following three radial distribution functions

D 3dxz, 3dyz 3dz2

Voting Card Question

Electrons in which orbital are shielded to the greatest extent?

Voting Card Question

Which has the largest radius?

Voting Card Question

E = Electron Affinity (EA)

Which is the least likely to give up an electron?

# of bonding electrons - # of antibonding electrons

What is the bond order of He2?

Goals for today:

1) Construct simple molecular

Deciding gerade vs. ungerade vs. neither

Molecular orbitals from atomic pz orbitals

Orbitals with the same energy are degenerate

Which orbital pairs are degenerate with each other?

A) #1/#2 and #3/#4

Constructing a molecular orbital diagram for all

Constructing a molecular orbital diagram for all

2pz 2px 2py

What is the bond order of O2?

Goals for today:

1) Review the cause and

2) Translate our knowledge of

Carbon monoxide MO diagram

How many bonds does carbon

Carbon monoxide MO diagram

A more complex heteronuclear orbital interaction: BF

A more complex heteronuclear orbital interaction: BF

Shown are two occupied orbitals

A more complex heteronuclear orbital interaction: BF

Where is the F located in the 1

Goals for today:

Voting Card Question

If three consecutive C4 operations are performed (denoted C43) on

Voting Card Question