QUANTUM MECHANICS

6
CHAPTER
AND ATOMIC STRUCTURE

6.1 Quantum Picture of the Chemical Bond

6.2 Exact Molecular Orbital for the Simplest Molecule: H2+
6.3 Molecular Orbital Theory and the Linear Combination
of Atomic Orbitals Approximation for H2+
6.4 Homonuclear Diatomic Molecules: First-Period Atoms
6.5 Homonuclear Diatomic Molecules: Second-Period
Atoms
6.6 Heteronuclear Diatomic Molecules
6.7 Summary Comments for the LCAO Method and
Diatomic Molecules

General Chemistry I
1
 Potential energy diagram for the decomposition of the methyl methoxy radical

General Chemistry I
2
 6.1 QUANTUM PICTURE OF THE CHEMICAL
BOND
 Potential energy of H2 (see section 3.7)

V = Ven + Vee + Vnn

 Using effective potential energy function, Veff or V(RAB)

- At large RAB, Veff → 0, and the atoms do not interact.
- As RAB decreases, Veff must become negative because of attraction.
- At very small RAB, Veff must become positive and large as Veff → ∞.

General Chemistry I
3
 Fig. 6.1
E0 : zero-point energy for the molecule
by the uncertainty principle
Dissociation energy: Do or De

General Chemistry I
4
 Changes in electron
density on formation
of H2 from 2H
(Fig. 6.2)

General Chemistry I
5
 Born-Oppenheimer Approximation: Slow
Nuclei, Fast Electrons
- Nuclei are much more massive than the electrons, the nuclei in the
molecules will move much more slowly than the electrons.

→ decoupling of the motions of the nuclei and the electrons

(A) Consider the nuclei to be fixed at a specific set of positions.

Then solve Schrödinger’s equation for the electrons moving around
and obtain the energy levels and wave functions.
Next, move the nuclei a bit, and repeat the calculation.
Continue this procedure in steps.

Each electronic energy level (E(el)) is related to the

nuclear coordinates, RAB.
: the proper set of quantum numbers)

General Chemistry I
6
General Chemistry I
7
 - Visualizing a group of electrons moving rapidly around the sluggish
nuclei, to establish a dynamic distribution of electron density (Fig. 6.3).

rapid movement effective potential

of the electrons energy functions

General Chemistry I
8
 Mechanism of
Covalent
Bond Formation
First phase

- When RAB → ∞,
independent H atoms

e-

General Chemistry I
9
- As the two atoms approach one
another,

Second phase

(The ‘particle in a box’ energies

decrease as the size of the box
increases)

e-

General Chemistry I
10
- As bond formation continues,

Third phase

e-

General Chemistry I
11
 Final phase

e-

General Chemistry I
12
 For the ionic bond, potential energy alone is essential. (section 3.8)

repulsion attraction

 For the covalent bond, the charge distribution and the kinetic energy
of the electrons are also important.

General Chemistry I
13
 6.2 EXACT MOLECULAR ORBITALS FOR THE
SIMPLEST MOLECULE: H2+

 H2+ ion: a single electron bound to two protons

bond length 1.06 Å; bond dissociation energy 2.79 eV = 269 kJ mol-1

- For a fixed value of RAB,

the position of the electron:

- The potential energy has cylindrical

(ellipsoidal) symmetry around the RAB axis.

General Chemistry I
14
  By the Born-Oppenheimer approximation,
- RAB : holding at the equilibrium bond length of 1.06 Å

Omitting  due to the same potential energy for all values of 

 The solution of the Schrödinger equation:

- smooth, single-valued, and finite in all regions of space

to define a probability density function of its square

Solutions exists when the total energy and angular momentum

are quantized.

General Chemistry I
15
 Electronic Wave Functions for H2+

1*u 2*u 3 g 3u*

1 g 2 g 1 u 1g*

- isosurface comprising the wave function with 0.1 of its maximum value.
- red: + amplitude; blue: - amplitude
- molecular orbital: each of exact one-electron wave functions

General Chemistry I
16
 Molecular orbital nomenclature

- Four labels summarize the energy and the shape of each wave function.

1) integer: an index tracking the relative energy

of the wave functions of each symmetry type.

i.e.) 1g: the first (the lowest energy) of the

1 g
g wave functions

2) Greek letter: how the amplitude of the wave

function is distributed around the internuclear axis.
- : the amplitude with cylindrical symmetry
around the axis 1 u
- : the amplitude with a nodal plane that contains
the internuclear axis

General Chemistry I
17
 3) g or u: how the wave function changes as we 2*u
invert our point of observation through the center
of the molecule (i.e. the wave function at (x, y, z)
and (-x, -y, -z):
g : symmetric, the same at these points
(‘gerade’)
u : antisymmetric, the opposite at these points
(‘ungerade’)
2 g

4) * : how the wave function changes when the

point of observation is reflected through a plane 1*u
perpendicular to the internuclear axis:

no * symbol : no changing sign upon reflection

(bonding MO)

•: changing sign upon reflection (antibonding

MO) 1 g
General Chemistry I
18
 Nature of the Chemical Bond in H2+

antibonding MO

bonding MO
General Chemistry I
19
 Summary of the Quantum Picture of
Chemical Bonding for H2+

1. The Born-Oppenheimer approximation: fixing the nuclei positions

2. Molecular orbital: one-electron wave function,

its square describes the distribution of electron density

3. Bonding MO: increased e density between the nuclei,

decreased effective potential energy

4. Antibonding MO: a node on the internuclear axis,

increased effective potential energy

5.  orbital: cylindrical symmetry; cross-sections perpendicular to the

internuclear axis are discs.

6.  orbital: has a nodal plane containing the internuclear axis

General Chemistry I
20
 6.3 MOLECULAR ORBITAL THEORY AND THE
LINEAR COMBINATION OF ATOMIC ORBITALS
APPROXIMATION FOR H2+
 LCAO method: selecting sums and differences (linear
combinations) of atomic orbital wave functions to generate
the best approximation to each type of molecular orbital
wave function
- The general form for H2+

General Chemistry I
21
  MOs of the  bonding

 The distribution of electron probability density

General Chemistry I
22
General Chemistry I
23
 Plots of
wave functions
and electron
probability
density for H2+
MOs
(Fig. 6.7)

General Chemistry I
24
 Energy of H2+ in the LCAO Approximation

g1s, RAB = 1.32 Å, D = 1.76 eV

g, RAB = 1.06 Å, D0 = 2.79 eV

Calculated by Burrau (1927):

from exact solutions of Schrödinger
equation

General Chemistry I
25
  Correlation diagram: the energy-level diagram
within the LCAO-MO model

General Chemistry I
26
 6.4 HOMONUCLEAR DIATOMIC MOLECULES:
FIRST-PERIOD ATOMS
For H2 and He2+,
 g1s  Cg  He1
A
  A
s   He1s   C g 1s  1s 
B B


 u*1s  Cu  He1

A
s   B

He1s   C 
g 1s A
 1s B


Fig. 6.11. Correlation diagram for H2. Fig. 6.12. Correlation diagram for He 2 .

General Chemistry I
27
 H2: Stabilization of bonding MO
by 2  (–E) for H2
compared to the
noninteracting system.

 He2+: Stabilization of bonding

MO by 2  (–E)
compensated by destabilization
of antibonding MO by +E .
 Net stabilization energy =
–E

General Chemistry I
28
  Bond order

Bond order = (1/2) x (number of electrons in bonding MOs

– number of electrons in antibonding MOs)

General Chemistry I
29
 6.5 HOMONUCLEAR DIATOMIC MOLECULES:
SECOND-PERIOD ATOMS

 LCAO-MO approximation

 Combination of 2s AOs to form g2s and u2s* MOs

 g 2 s  Cg [2 s A  2 s B ]
 u*2 s  Cu [2 s A  2 s B ]

 Combination of 2pz AOs to form  g 2 pand  u 2 pz MOs

*
z

 g 2 pz  C g [2 pzA  2 pzB ]
 u*2 pz  Cu [2 pzA  2 pzB ]
The core 1s2 electrons are not included – they are too low in
energy
General Chemistry I
30
 Rules for LCAO-MO Model (Mulliken)
1. Only AOs of the same symmetry along the bond axis can
be combined to give MOs.

+ OR + OR

+ OR OR

+ +

2. AOs of the same or similar energies will interact more

strongly than those of widely different energies.
General Chemistry I
31
 new node

 g2 p
Fig. 6.14 Formation of (a) bonding
z
and (b) antibonding MOs
from 2pz orbitals on atoms A and B.

General Chemistry I
32
  Doubly degenerate  2 p&x  u 2 pMOs
y

 u 2 px  Cu [2 pxA  2 pxB ]
 g* 2 px  Cg [2 pxA  2 pxB ]

 u 2 py  Cu [2 p yA  2 p yB ] new node

 g* 2 p y  Cg [2 p yA  2 p yB ]

General Chemistry I
33
  Determination of energy ordering

1. Average energy of bonding-antibonding pair of MOs

similar to that of original AO’s

2. Energy difference between a bonding-antibonding pair

becomes large as the overlap of AO’s increases

3. Rule of thumb 1: bonding MOs < antibonding MOs

4. Rule of thumb 2: energy increases with number of nodes

5. Ordering for -group: 2s < 2s* < 2p < 2p* (see slide 35)

6. Ordering for-group: 2p < 2p* (see slide 35)

7. For ordering  and , experimental results must be invoked:

2p < 2p, 2p* < 2p* for all the 2nd-row molecules (except O2 and F2)
2p < 2p, 2p* < 2p* for O2 and F2 (see slide 36, etc)
General Chemistry I
34
 Energy ordering of and  MO types

Energy
increases
with the
no. of
nodes in
the same
symmetry.

σ-MOs π-MOs Box wave functions

General Chemistry I
35
 Fig. 6.16 Energy levels for the homonuclear diatomics Li2 through F2.

General Chemistry I
36
 HOMO =
LUMO Highest
LUMO HOMO (energy)
Occupied MO

HOMO
LUMO =
Lowest
(energy)
Unoccupied
MO

Fig. 6.17 Correlation diagrams for second-period diatomic

molecules, N2 & F2.

General Chemistry I
37
 Correlation diagram and corresponding
MOs for N2
u2pz

u2px , u2py

g2pz

u2px , u2py

g2s

g2s

General Chemistry I
38
 Correlation diagram and corresponding
MOs for F2 u2pz

u2px , u2py

u2px , u2py

g2pz

g2s

g2s

General Chemistry I
39
  Cross-over in the correlation diagrams of Li2~N2 and O2~Ne2

 Reversed ordering of energy for Li2 ~ N2

 g 2 pz   u 2 px (or  u 2 p y )

~ Due to large electron-electron spatial repulsions between

 g 2 pz  u*2 s
electrons in and MO’s.

 Normal ordering of energy for O2, F2, Ne2

 g 2 pz   u 2 px (or  u 2 p y )

~ As Z increases, the repulsion decreases since electrons

 g 2 s and  u*2 s
in MO’s are drawn more strongly toward

the nucleus.

General Chemistry I 4040

 Fig. 6.18 (a) Paramagnetic liquid oxygen, O2, and (b) diamagnetic
liquid nitrogen, N2, pours straight between the poles of a magnet.

paramagnetic
General Chemistry I
41
 Fig. 6.19 Trends in several properties with the number of valence
General Chemistry
electrons I
in the second-row diatomic molecules.
42
 6.6 HETERONUCLEAR DIATOMIC
MOLECULES

For the 2s orbitals,

2s = CA2sA + CB2sB 2s* = CA’2sA – CB’2sB

In the homonuclear case, CA = CB; CA’ = CB’

If B is more electronegative than A,

CB > CA for bonding  MO,

CA’ > CB’ for the higher energy * MO,

A
closely resembling a 2sA AO
B

General Chemistry I
43
 B O

Fig. 6.20 Correlation

diagram for
heteronuclear
diatomic
molecule, BO. (O is
more electronegative)

LCAO/MO electron
configuration:

(2s)2(*2s)2(2px)2(2py)2(2pz)1

General Chemistry I
44
 
+1sH +2pFz
Fig. 6.21
(d) Overlap
of
atomic
nb orbitals
+1s +2p
H F
x,y in HF.
(c)

+1sH –2pFz 

(b)

( +1sH +2sF nb

(
a (a)
General
) Chemistry I
45
 Fig. 6.22 Correlation
diagram for HF. The
2s, 2px, and 2py
atomic orbitals of F
do not mix with the
1s atomic orbital of H,
and therefore remain
nonbonding.
LCAO/MO electron
configuration:

General Chemistry I
46
 6.7 SUMMARY COMMENTS FOR THE LCAO-
MO METHOD AND DIATOMIC MOLECULES

The qualitative LCAO-MO method easily identifies the sequence

of energy levels for a molecule, such as trends in bond length
and bond energy, but does not give their specific values.

The qualitative energy level diagram is very useful for

interpreting experiments that involve adsorption and
emission of energy such as spectroscopy, ionization by
electron removal, and electron attachment.

General Chemistry I
47
 QUANTUM MECHANICS
6
CHAPTER
AND ATOMIC STRUCTURE

6.8 Valence Bond Theory and the Electron Pair Bond

6.9 Orbital Hybridization for Polyatomic Molecules
6.10 Predicting Molecular Structures and Shapes
6.11 Using the LCAO and Valence Bond Methods Together
6.12 Summary and Comparison of the LCAO and Valence
Bond Methods
6.13 A Deeper Look (Properties of Exact Molecular Orbitals
for H2+)

General Chemistry I
48
 6.8 VALENCE BOND THEORY AND THE
ELECTRON PAIR BOND

 Explains the Lewis electron pair model

 VB wave function for the bond is a product of two
one-electron AO wave functions
 Easily describes structure and geometry of bonds
in polyatomic molecules

Nobel Prizes
Chemistry (‘54)
“The Nature of
Chemical
Bonding”
Peace (‘62)

Walther Heitler Fritz London John C. Slater Linus Pauling

(DE, 1904-1981) (DE, 1900-1954) (US, 1900-1976) (US,1901-1994)
General Chemistry I
49
  Single Bonds

- At very large values of RAB,

independent atoms

- As the atoms begin to interact strongly,

(Electrons are now indistinguishable)

General Chemistry I
50
 VB wave function for the single bond in a H2 molecule

 gel  C1 1s A (1)1s B (2)  1s A (2)1s B (1)   Bonding MO

 uel  C1 1s A (1)1s B (2)  1s A (2)1s B (1)   Antibonding MO

Fig. 6.24 (a) The electron density g for gel and u for uel in the simple
VB model for H2. (b) Three-dimensional isosurface of the electron density
for the gel wave function in the H2  bond.

General Chemistry I
51
  For F2  bond,

 For HF  bond,

General Chemistry I
52
  Multiple Bonds

N: (1s)2(2s)2(2px)1(2py)1(2pz)1

General Chemistry I
53
  Polyatomic Molecules

all C-H
bonds
equivalent
? (from
experiment)

 Electron promotion: electron relocated to a higher-energy orbital

promotion hybridization

General Chemistry I
54
 6.9 ORBITAL HYBRIDIZATION FOR
POLYATOMIC MOLECULES
 sp-Hybridization BeH2
Promotion: Be: (1s)2(2s)2  Be: (1s)2(2s)1(2pz)1
Two equivalent sp hybrid orbitals:

1 1
1 (r )   2 s  2 pz  and  2 (r )   2 s  2 pz 
2 2

New electronic configuration, Be: (1s)2(1)1(2)1

Wave functions for the two bonding pairs of electrons:

 bond  
1 (1, 2)  c  1 (1)1s (2)  1 (2)1s (1) 
H H

 bond
2 (3, 4)  c  
  2 (3)1s H
(4)   2 (4)1s H
(3) 

A pair of  bonds at an angle 180o apart  linear molecule

General Chemistry I
55
 Fig. 6.28 Formation, shapes, and bonding of the sp hybrid orbitals in the
BeH2 molecule. (a) The 2s and 2pz orbitals of the Be atom. (b) The two sp
hybrid orbitals formed from the 2s and 2pz orbitals on the Be atom. (c) The
two  bonds that form from the overlap of the sp hybrid orbitals with the
H1s orbitals, making two single bonds in the BeH 2 molecule. (d) Electron
density in the two  bonds.

General Chemistry I
56
 sp2-Hybridization BH3

Promotion: B: (1s)2(2s)2(2px)1  B: (1s)2(2s)1(2px)1(2py)1

Three equivalent sp2 hybrid orbitals:

1 (r )  2s  (1/ 2)1/ 2 2 p y
 2 (r )  2 s  (3 / 2)1/ 2 2 px  (1/ 2)1/ 2 2 p y
 3 (r )  2 s  (3 / 2)1/ 2 2 px  (1/ 2)1/ 2 2 p y

New electronic configuration, B: (1s)2(1)1(2)1(3)1

Three bonds at an angle 120o in a plane  trigonal planar

General Chemistry I
57
 Fig. 6.29
Formation,
shapes, and
bonding of
the sp2
hybrid
orbitals in
the
BH3
molecule

General Chemistry I
58
 sp3-Hybridization CH4

Promotion: C: (1s)2(2s)2(2px)1(2py)1  C: (1s)2(2s)1(2px)1(2py)1(2pz)1

Four equivalent sp3 hybrid orbitals:

1
1 (r )   2 s  2 px  2 p y  2 pz 
2
1
 2 (r )   2s  2 px  2 p y  2 pz 
2
1
 3 (r )   2s  2 px  2 p y  2 p z 
2
1
 4 (r )   2s  2 px  2 p y  2 pz 
2

New electronic configuration, C: (1s)2(1)1(2)1(3)1 (4)1

Four bonds at an angle 109.5o generating tetrahedral geometry

General Chemistry I
59
 Fig. 6.30 Shapes and relative orientations of the four sp3 hybrid orbitals
in CH4 pointing at the corners of a tetrahedron with the C atom at its center.

General Chemistry I
60
 Summary of Hybridization Results

General Chemistry I
61
 Hybridization and Lone Pairs

 NH3: sp3 hybrid orbitals

trigonal pyramid with three equivalent

bonds

 H2O: sp3 hybrid orbitals

two lone pairs → bent or angular

structure

General Chemistry I
62
  Multiple Bonds in Organic Compounds

 Ethylene, C2H4

Promotion, C: (1s)2(2s)2(2px)1(2py)1  C: (1s)2(2s)1(2px)1(2py)1(2pz)1

Formation of three sp2 hybrid orbitals from the 2s and two 2p orbitals
New electronic configuration, C: (1s)2(1)1(2)1(3)1(2pz)1

Five  bonds: C11-H1s, C12-H1s, C21-H1s, C21-H1s, C13- C23

One  bond: C12pz-C22pz

One double bond (C=C): (C13- C23) + (C12pz-C22pz)

Note:  = sp2

General Chemistry I
63
 Fig. 6.33 Formation of  bonds in ethylene.

Fig. 6.34 Formation of a  bond in ethylene.

General Chemistry I
64
  Acetylene, C2H2

Linear, triple bond, H-C-C bond angles of 180o

Promotion, C: (1s)2(2s)2(2px)1(2py)1  C: (1s)2(2s)1(2pz)1(2px)1(2py)1

Formation of two sp hybrid orbitals from the 2s and the 2pz orbitals

New electronic configuration, C: (1s)2(1)1(2)1(2px)1(2py)1

Three  bonds: C11-H1s, C21-H1s, C12- C22

Two  bonds: C12px-C22px, C12py-C22py

One triple bond :  (C12- C22) +  (C12px-C22px, C12py-C22py)

Note:  = sp

General Chemistry I
65
 Fig. 6.35 Formation of  bonds in acetylene.

Fig. 6.36 Formation of two  bonds in acetylene.

General Chemistry I
66
 6.10 PREDICTING MOLECULAR
STRUCTURES AND SHAPE

 Description of the structure and shape of a molecule

(1) Determine the empirical formula.

(2) Determine the molecular formula.
(3) Determine the structural formula from a Lewis diagram.
(4) Determine the molecular shape from experiments.
(5) Identify the hybridization scheme that best explains
the shape predicted by VSEPR.

General Chemistry I
67
EXAMPLE 6.4
Hydrazine: Elemental analysis shows its mass per cent composition to be
87.419% nitrogen and 12.581% hydrogen. The density of hydrazine at 1 atm
And 25 oC is 1.31 gL-1. Determine the molecular formula for hydrazine.
Predict the structure of hydrazine. What is the hybridization of the N atoms?

(1) Elemental analysis: N(87.419%), H (12.581%)

(2) Empirical formula: NH2  (Molar mass)emp
(3) Molar mass calculated from the ideal gas law (with known )
(4) Molar mass / (Molar mass)emp = 2, Molecular formula: N2H4
(5) Lewis diagram, steric number (4)  sp3 hybrid orbitals

General Chemistry I
68
General Chemistry I
69
The electrostatic
potential energy map

Fig. 6.38 (a) Space-filling

models. (b) 0.002 e/(a0)3
electron density surfaces,
and (c) electrostatic
potential energy surfaces.

General Chemistry I
70
 6.11 USING THE LCAO AND VALENCE BOND
METHODS TOGETHER

 Linear Triatomic Molecules (CO2, N2O, NO2+)

 Central atom  sp hybridization from s and pz orbitals

Two sp orbitals form  bonds with outer atoms
Remaining px and py orbitals form  bonds

  bonds  pz orbital (outer atom) with sp hybrid (central atom)

  bonds  linear combinations of the px (or py) orbitals give

bonding, antibonding, and nonbonding

General Chemistry I
71
 Fig. 6.40
-bonding
in linear
triatomic
molecules

General Chemistry I
72
 Fig. 6.41 Correlation diagram for -
electrons in linear triatomic molecules
(for CO2)

General Chemistry I
73
 Nonlinear Triatomic Molecules (NO2, O3, NF2, NO2-)

 Central atom  sp2 hybridization from s, px, and py orbitals

One of sp2 orbitals holds a lone pair
Two of sp2 orbitals form  bonds with outer atoms
Remaining pz orbital forms  bond
 Outer atom
p orbital pointing toward the central atom forms a  bond
pz orbital forms a  bond with pz orbitals of other atoms
Remaining p orbital and s orbital  nonbonding

General Chemistry I
74
 Fig. 6.42 (a) Ball-and-stick model (bottom) and 
molecular orbitals for bent triatomic molecule, NO 2–,
with three sp2 hybrid orbitals on the central N atom
that would lie in the plane of the molecule.
(b) Correlation diagram for the  orbitals. There is
only one of each of MO (, nb, *).
General Chemistry I
75
 6.12 SUMMARY AND COMPARISON OF THE
LCAO AND VALENCE BOND METHODS

 LCAO method for H2 forming a  bond:

 g1s  Cg 1As  1Bs  
 1s A  1s B 

 Molecular electronic wave function in the LCAO

approximation:
 MO   g1s (1) g1s (2)  1s (1)  1s (1)  1s (2)  1s (2) 
el A B A B

 MO
el
 1s A (1)1s B (2)  1s A (2)1s B (1)   1s A (1)1s A (2)  1s B (1)1sB (2) 

General Chemistry I
76
 Molecular electronic wave function in the VB model:
 VB
el
(r1A , r2B )  c1 A (r1A ) B ( r2B )  c2A ( r2A ) B ( r1B )   VB
el
 1s A (1)1s B (2)  1s A (2)1s B (1)

 Comparison of MO and VB theories:

 MO
el
 1s A (1)1s B (2)  1s A (2)1s B (1)   1s A (1)1s A (2)  1s B (1)1s B (2) 
                       
el
 VB  ionic

purely covalent structure mixture of ionic states,

H–H HA-HB+ and HA+HB-

 Improved VB wavefunction: This is over-emphasized

in original LCAO-MO
 improved   VB   ionic method and is absent
in original VB model

General Chemistry I
77
General Chemistry I
78
 10 Problem Sets

For Chapter 6,

2, 18, 28, 48, 52, 58, 62, 64, 66, 72

General Chemistry I
79