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QUANTUM MECHANICS
AND MOLECULAR STRUCTURE

CHAPTER

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
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Potential energy diagram for the decomposition of the methyl methoxy radical

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6.1 QUANTUM PICTURE OF THE CHEMICAL

BOND
Specific example of H2, (in section 3.7)
V=V = Ven + Vee + Vnn

Using effective potential energy function, Veff

- 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 .
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E0 : zero-point energy for the molecule
by the uncertainty principle
Dissociation energy: Do or De

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effective potential
energy function

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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 Schrdingers 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.
Getting each electronic energy

to the nuclear coordinates RAB

: the proper set of quantum numbers

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(B) Consider the function
to be the attractive portion.
Add the repulsive interaction to
obtain the effective potential
energy curve.

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- Visualizing a group of electrons moving rapidly around the sluggish
nuclei, to establish a dynamic distribution of electron density.
rapid movement
of the electrons

effective potential
energy functions

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Mechanism of Covalent
Bond Formation
The average value of

241

- When RAB ,
independent H atoms
e-

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- As the two atoms approach one another,
increases;
the Coulomb attraction reduces between
each electron and the proton to which it
was originally bound .
decreases;
each electron becomes less confined.
(The energy of the particle in a box
decrease as the size of the box
increases)
decreasing the
e-

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- As bond formation continues,
decreases;
the simultaneous Coulomb attraction
of each electron to two protons
decreases the average potential energy.
increases;
confinement of the electron to the
smaller internuclear region increases
its kinetic energy.
decreasing the

e-

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- The minimum in the

, and the
equilibrium bond length of the molecule,
is determined by the competition between
the increasing average kinetic energy
and the decreasing average potential
energy at small values of internuclear
separation.

e-

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For the ionic bond, potential energy alone is essential. (section 3.8)
V(R12) = Ae-R12 - B

+ E

repulsion attraction

For the covalent bond, the charge distribution and the kinetic energy of
the electrons are also important.
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6.2 EXACT MOLECULAR ORBITALS FOR THE

SIMPLEST MOLECULE: H2+
H2+ ion: a single electron bound to two protons
bond length 1.06 ; bond dissociation energy 2.79 eV = 269 kJ mol-1

V = -

= Ven + Vnn

- For a fixed value of RAB,

the position of the electron:
, ,
, ,
- The potential energy has cylindrical
(ellipsoidal) symmetry around the RAB axis.

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By the Born-Oppenheimer approximation,
- RAB : holding at the equilibrium bond length of 1.06
-

, ;

: the electronic wave function for the electrons

Omitting due to the same potential energy for all values of

The solution of the Schrdinger equation:
- smooth, single-valued, and finite in all regions of space
to define a probability density function of its square
- physical boundary conditions
0 as and as
Solutions exists when the total energy and angular momentum
are quantized.

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Electronic Wave Functions for H2

- 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
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- 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.) 1g: the first (the lowest energy) of the
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
- : the amplitude with a nodal plane that contains
the internuclear axis

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3) g or u: how the wave function changes as we
invert our point of observation through the center
of the molecule
- 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
4) * : how the wave function changes when the
point of observation is reflected through a plane
perpendicular to the internuclear axis
- no symbol : no changing sign upon reflection
* : changing sign upon reflection

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Nature of the Chemical Bond in H2

antibonding MO

bonding MO
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Summary of the Quantum Picture of

Chemical Bonding
1. The Born-Oppenheimer approximation: fixing the nuclei position
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
high effective potential energy
5. orbital: cylindrical symmetry; cross-sections perpendicular to the
internuclear axis are discs.
6. orbital: a nodal plane containing the internuclear axis

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6.3 MOLECULAR ORBITAL THEORY AND THE

LINEAR COMBINATION OF ATOMIC ORBITALS
APPROXIMATION FOR H2+

248

LCAO method: selecting sums and differences (linear

combinations) of atomic orbitals to generate the best
approximation to each type of molecular orbital
- The general form for H2+

: generic wave function
: wave function of atomic orbitals
The two nuclei are identical, then

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MOs of the bonding

The distribution of electron probability density

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Energy of H2+ in the LCAO Approximation

251

g1s, RAB = 1.32 , D = 1.76 eV

g, RAB = 1.06 , D0 = 2.79 eV

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Correlation diagram: the energy-level diagram within the LCAO

251

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6.4 HOMONUCLEAR DIATOMIC MOLECULES:

FIRST-PERIOD ATOMS

252

For He2+ and He2,

A
B
B

g1s Cg He1
s He1s C g 1s 1s

A
B
B

u*1s Cu He1
s He1s C g 1s 1s

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

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6.5 HOMONUCLEAR DIATOMIC MOLECULES:

SECOND-PERIOD ATOMS
LCAO-MO approximation
Combination of 2s AOs to form g2s and u2s* MOs

g 2 s C g [2 s A 2 s B ]
u*2 s Cu [2 s A 2 s B ]
*
Combination of 2pz AOs to form g 2 p and u 2 p MOs
z

g 2 p C g [2 pzA 2 pzB ]
z

*
u 2 pz

Cu [2 pzA 2 pzB ]

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Fig. 6.14. Formation of (a) g 2 p bonding and (b) u 2 pz antibonding MOs

from 2pz orbitals on atoms A and B.
*

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Doubly degenerate 2 px & u 2 p MOs

y

u 2 p Cu [2 pxA 2 pxB ]
x

*
g 2 px

C g [2 pxA 2 pxB ]

u 2 p Cu [2 p yA 2 p yB ]
y

*
g 2 py

C g [2 p yA 2 p yB ]

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Determination of energy ordering

1. Average energy of bonding-antibonding pair of MOs
similar to that of original AOs
2. Energy difference between a bonding-antibonding pair
becomes large as the overlap of AOs increases

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Fig. 6.16. Energy levels for the homonuclear diatomics Li2 through F2.
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Fig. 6.17. Correlation diagrams for second-period diatomic molecules, N2 & F2.
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Cross-over in the correlation diagrams of Li2~N2 and O2~Ne2

Reversed ordering of energy for Li2 ~ N2

g 2 p u 2 p (or u 2 p )
z

~ Due to large electron-electron spatial repulsions between

*
electrons in g 2 p and u 2 s MOs.
z

Normal ordering of energy for O2, F2, Ne2

g 2 p u 2 p (or u 2 p )
z

~ As Z increases, the repulsion decreases since electrons

*
in g 2 s and u 2 s MOs are drawn more strongly toward

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

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Fig. 6.19. Trends in several properties with the number of valence electrons in
the second-row
diatomic
molecules.
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6.6 HETERONUCLEAR DIATOMIC

MOLECULES

262

For the 2s orbitals,

2s = CA2sA + CB2sB

2s* = CA2sA CB2sB

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

If B is more electronegative than A,
CB > CA for bonding s MO,
CA > CB for the higher energy s* MO,
closely resembling a 2sA AO

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Fig. 6.20. Correlation diagram for heteronuclear diatomic

molecules,
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Fig. 6.22. Correlation diagram for HF. The 2s, 2px, and 2py atomic orbitals of
F do notChemistry
mix with theI 1s atomic orbital of H, and therefore remain nonbonding.
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Fig. 6.21. Overlap of

atomic orbitals in HF.

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6.7 SUMMARY COMMENTS FOR THE LCAO

METHOD AND DIATOMIC MOLECULES
The qualitative LCAO 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.

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QUANTUM MECHANICS
AND MOLECULAR STRUCTURE

CHAPTER

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

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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 AOs
Easily describes structure and geometry of bonds
in polyatomic molecules

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Single Bonds
- At very large values of RAB,

;
independent atoms

- As the atoms begin to interact strongly,

indistinguishable

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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
el
for the Chemistry
in the H2 bond.
g wave function
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For F2 bond,

1 2

1 1

2 2

For HF bond,

2 1

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

1,2

1 2

2
2

1,2

2 2

1 2
2
2 2
1
1 2

2 2

2
1

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Polyatomic Molecules

all C-H
bonds
equivalent

Electron promotion: electron relocated to a higher-energy orbital

promotion

hybridization

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6.9 ORBITAL HYBRIDIZATION FOR

POLYATOMIC MOLECULES
sp-hybridization

273

BeH2

Promotion: Be: (1s)2(2s)2 Be: (1s)2(2s)1(2pz)1

Two equivalent sp hybrid orbitals:
1 (r )

1
1
2s 2 pz and 2 (r ) 2 2s 2 pz
2

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

Wave functions for the two bonding pairs of electrons:
H
H

bond
1 (1, 2) c 1 (1)1s (2) 1 (2)1s (1)
H
H

bond
2 (3, 4) c 2 (3)1s (4) 2 (4)1s (3)

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

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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 tow single bonds in the BeH2 molecule. (d) Electron
density in the two bonds.
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BH3

sp2-hybridization

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

Three equivalent sp2 hybrid orbitals:
2

3/2

1/2

3/2

1/2

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

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

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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
2
1
2 (r ) 2 s 2 px 2 p y 2 pz
2
1
3 (r ) 2 s 2 px 2 p y 2 pz
2
1
4 (r ) 2 s 2 px 2 p y 2 pz
2

1 (r ) 2 s 2 px 2 p y 2 pz

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

Four bonds at an angle 109.5o generating tetrahedral geometry

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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.

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Summary of Hybridization Results

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Hybridization and Lone Pairs

NH3: sp3 hybrid orbitals
trigonal pyramid with three equivalent
bonds

H2O: sp3 hybrid orbitals

two lone pairs the bent or angular
structure

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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: C11-H1s, C12-H1s, C21-H1s, C21-H1s, C13- C23
One bond: C12pz-C22pz
One double bond (C=C): (C13- C23) + (C12pz-C22pz)

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Fig. 6.33. Formation of bonds in ethylene.

Fig. 6.34.
Formation of a bond in ethylene.
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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(2px)1(2py)1(2pz)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: C11-H1s, C21-H1s, C12- C22
Two bonds: C12px-C22px, C12py-C22py
One triple bond : (C12- C22) + (C12px-C22px, C12py-C22py)

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Fig. 6.35. Formation of bonds in acetylene.

Fig. 6.36.
Formation of two bonds in acetylene.
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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.

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EXAMPLE 6.4
Hydrizine: 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 calculate 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

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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.
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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 forms bond
bonds pz orbital (outer) with sp hybrid (central)
bonds linear combinations of the px (or py) orbitals
bonding, antibonding, and nonbonding

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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

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Fig. 6.42. (a) Ball-and-stick model (bottom) and

molecular orbitals for bent triatomic molecule, NO2,
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 orbitals (, nb, *).

290

6.12 SUMMARY AND COMPARISON OF THE

LCAO AND VALENCE BOND METHODS
LCAO method for H2 forming a bond:
1s A 1s B
g1s C g 1As 1Bs

Molecular electronic wave function in the LCAO approximation:

el
MO
g1s (1) g1s (2) 1s A (1) 1s B (1) 1s A (2) 1s B (2)

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)
MO

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Molecular electronic wave function in the VB model:

el
el
VB
( r1A , r2B ) c1 A ( r1A ) B (r2B ) c2 A ( r2A ) B ( r1B ) VB
1s A (1)1s B (2) 1s A (2)1s B (1)

Comparison of MO and VB theories:

1

1 1

2 1

purely covalent structure

HH

1 1

1 1

mixture of ionic states,

HA-HB+ and HA+HB-

Improved VB wavefunction:

improved VB ionic

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10 Problem Sets

For Chapter 6,
2, 18, 28, 48, 52, 58, 62, 64, 66, 72

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