Chapter 03

General Chemistry I (2022) Lecture by B. H.
Hong
Chapter 03. MOLECULAR SHAPE AND STRUCTURE

General Chemistry I (2022) Lecture by B. H. Hong
2



Key Ideas Simple: Electrostatic repulsion between electron pairs

Quantum mechanical: Valence-bond theory & molecular
orbital theory
Goal Molecular shape ⇒ Chemical properties
THE VSEPR MODEL

3.1 The Basic VSEPR Model
3.2 Molecules with Lone Pairs on the Central Atom
3.3 Polar Molecules
VALENCE-BOND THEORY
3.4 Sigma and Pi Bonds
3.5 Electron Promotion and the Hybridization of Orbitals
3.6 Other Common Types of Hybridization
3.7 Characteristics of Multiple Bonds
MOLECULAR ORBITAL THEORY

3.8 The Limitations of Lewis’s Theory
3.9 Molecular Orbitals
3.10 The Electron Configurations of Diatomic Molecules
3.11 Bonding in Heteronuclear Diatomic Molecules
3.12 Orbitals in Polyatomic Molecules
IMPACT ON MATERIALS:
ELECTRONIC CONDUCTION IN SOLIDS
3.13 Bonding in the Solid State
3.14 Semiconductors
THE VSEPR MODEL General Chemistry I (2022) Lecture by B. H. Hong
THE VSEPR MODEL

3D structure of a molecule is crucial for its property.
Sophisticated quantum mechanical calculations are needed

to predict the structure.
⇒ Computer-aided "rational drug design"
Box 3.1
1) Identification of key enzymes
2) Molecular structure determination
3) Computer-aided design of molecules

with structures fitting into the active site

Valence Shell Electron-Pair Repulsion theory
Electron pairs (lone pairs & bonding pairs) repel each other.
Rule 1: Electron pairs move as far apart as possible.
Rule 2: (Almost) No distinction between single and

multiple bonds.
VSEPR structures for AXn with no lone pair Fig 3.2

R. J. Gillespie, Chem. Soc. Rev. 21, 59-69, (1992).
Nitrate (NO3–)
Ethene (ethylene; C2H4)
The double bond repels more than

the single bonds.
Rule 3: Only the positions of atoms are considered when

reporting the molecular shape.
Ex 3.2 NF3; trigonal pyramidal
Rule 4: For a given angle,

lone pair–lone pair > lone pair–atom > atom–atom Fig 3.3

Rule 5: Smaller angle >> larger angle
Distortions in NH3, H2O, CH3Cl
Lone pairs occupy more space (solid angle) near the center
than bonding pairs.
Cl is more electronegative than H;

Cl occupies less space near the center than H.

Lone pairs and distortions in trigonal bipyramidal
structures; PF5, SF4, ClF3, XeF2

AXE method
A; central atom
X; outside atom
E; lone pair
Fig 3.7

3.3 Polar Molecules
Nonpolar molecule; zero net electric dipole moment
Homonuclear diatomic molecules
Polyatomic molecules with symmetry;

CO2, BF3, CH4, CCl4, trans-dichloroethane, ···
Polar molecule; nonzero electric dipole moment

HCl, H2O, CHCl3, cis-dichloroethane, ···
VALENCE-BOND THEORY General Chemistry I (2022) Lecture by B. H. Hong
Valence-Bond theory
Lewis model of the chemical bond; localized electron model

Valence-bond theory; Walter Heitler, Fritz London (1927)
Quantum mechanical description of the distribution of electrons in

bonds
Valence electrons are localized either between pairs of

atoms or on atoms as lone pairs.
1) Hybridization of atomic valence orbitals with proper

symmetry that are localized between pairs of atoms
2) Placing valence electrons in the hybridized orbitals

as pairs (↑↓) or leaving them localized in lone-pair orbitals on
individual atoms in the molecule
H2
1) Two hydrogen 1s-orbitals merge to form a
between the two hydrogen atoms.
2) A is formed as two electrons (↑↓) fill the .
Fig 3.8
; cylindrically symmetrical with no nodal planes

containing the intermolecular axis
HF
Fig 3.9
N2
2
;
single nodal plane containing
the intermolecular axis.
Two and
bonds merge to form a long
donut-shape electron cloud.
Fig 3.12
CH4; tetrahedral
1) Promotion of a 2s-electron to an empty 2p;
small energy difference between 2s and 2p & less repulsion
C: [He]2s22px12py1 C: [He]2s12px12py12pz1
⇒ Tetravalence of carbon
N, O, and F cannot use promotion to increase valency

(no empty p-orbitals).
Boron, [He]2s22p1, typically forms three bonds

by promoting one 2s-electron.

2) sp3 hybrid orbitals of equal energy Figs 3.13, 3.16c
4 sp3 hybrid orbitals are pointing toward the corners

of a tetrahedron.
Figs 3.13 Figs 3.16c

Fig 3.14
3) Hybridization (overlapping) of
each sp3 orbital with an H 1s-orbital
to form a .

Fig 3.15
C2H6; ethane, 2 central C atoms
NH3; tetrahedral electron-pair arrangement

of sp3 hybridization
BF3; trigonal planar Fig 3.16b
sp2 hybrid orbitals

Fig 3.16a
CO2; linear
sp hybrid orbitals
PCl5; trigonal bipyramidal

sp3d hybrid orbitals
Fig 3.17
SF6, XeF4; octahedral electron arrangement

sp3d2 hybrid orbitals Fig 3.18
Tab 3.2 Hybridization and molecular shape
N atomic orbitals produce N hybrid orbitals.
Terminal atoms (except H) are also

sp3 hybridized.

C, N, and O in Period 2 readily form double bonds

via 2p-2p hybridization.
Elements in Period 3 or later rarely form double bonds due
to long bond length.
CH2=CH2; planar
C=C double bond; ,
resistant to twisting
C–H bond;
C=C bonds prevent free rotation of the C–C bonds.
3-D structure of a molecule
Fig 3.19
C6H6; planar hexagonal ring

C6-ring bond; , planar Fig 3.20
C=C bond;
three -bonds over the hexagonal ring Fig 3.21
Resonance of the two Kekulé structures

6 electrons are spread around the entire ring. Fig 3.22
HC CH (ethyne, acetylene); linear
C C triple bond;
Fig 3.23
C–H bond;
MOLECULAR ORBITAL THEORY General Chemistry I (2022) Lecture by B. H. Hong
3.8 The Limitations of Lewis's Theory

3.9 Molecular Orbitals
The valence-bond (VB) and molecular orbital (MO) theories are both
procedures for constructing approximate wavefunctions of electrons.
The MO theory can account for electron-deficient compounds,

paramagnetic O2, and many other properties by focusing on electrons
delocalized over the whole molecule.
The VB theory focuses on electrons on individual bonds between pairs

of atoms.
MOLECULAR ORBITAL THEORY Fredrich Hund, Robert Mulliken (1966)
Box 3.2 Magnetism; diamagnetic, paramagnetic,

ferromagnetic, antiferromagnetic, ferrimagnetic
Paramagnetic O2; unpaired electron(s) Fig 3.24
Lewis's theory;
Valence-bond theory;
bond and bond
2 lone pairs on each O occupying the sp2 hybrid orbitals
B2H6 (diborane); electron-deficient compound
At least seven bonds (= 14 electrons) are required,

but only 12 valence electrons.
Linear combination of atomic orbitals molecular orbital (LCAO-MO) method
Approximate molecular wavefunctions by superimposing (mixing) of N

atomic orbitals
cij and Ej are determined

by solving the Schrödinger equation

Trial wavefunctions for H2 using two 1s atomic orbitals of H
Increased amplitude in the internuclear region bonding

Larger volume for electrons
lower kinetic energy
(particle-in-a-box)
Decreased amplitude in the internuclear

region & nodal plane
antibonding

Molecular orbital energy level diagram Fig 3.27
Box 3.3 Photoelectron spectroscopy;

orbital energies from EK of
photoelectrons

Building-up principle for MO
1. Lower to higher
2. Up to two electrons (↑↓) per MO; Pauli exclusion principle
3. Hund's rule
H2: Fig 3.28

The energy of H2 is lower than that of the separate H atoms.
Even the energy of H2+ is lower than that of

the separate H atoms.


Homonuclear diatomic molecules of Period 2
Linear combination of 10 atomic orbitals;
1. No mixing between AO's of the same atom
2. Significant mixing only between AO's of similar energies

and substantial overlap
⇒ Negligible mixing between the core 1s and the valence

2s and 2p orbitals
⇒ No MO from 2s–2p mixing due to symmetry



Molecular orbital energy level diagram

(obtained from the Schrödinger equation)
The energy separation of 2s and 2p for O2 and F2 are large due to

large Zeff pulling 2s-electrons closer.
⇒ Negligible 2s-2p mixing for O2 and F2


Bond order
Nonpolar covalent bond;
Ionic bond (A+B–);
Polar covalent bond;

if A is more electronegative. Fig 3.33

HF
No net overlap between H1s and (F2px or F2py)

⇒ 2 "nonbonding" orbitals
orbital mainly of F2pz (energy level close to F2pz)
orbital mainly of H1s (energy level close to H1s)
⇒
CO and NO Fig 3.35
from 2p-2p mixing only

H2O;
1b1; nonbonding, mainly O2py, lone pair effect

2a1; almost nonbonding
⇒
CH4; 1 of the 4 electron pairs is slightly lower in energy.

⇒ photoelectron spectroscopy
VB-theory; all eight electrons have the same energy.
MO-theory; (1a1)2(1t1)6
⇒ Lower energy for the 1a1 electron pair
C6H6 = 30 atomic orbitals
VB theory for delocalized in the ring plane
from 24 AO's = 6 (C2s, C2px, C2py, H1s)
⇒ sp2 hybridization for
MO theory for the delocalized

6 from 6 C2pz
⇒

Electron-deficient molecules
No need to provide one pair of electrons for each pair of atoms
⇒ Existence of electron-deficient molecules such as B2H6
SF6; hypervalent compounds
VB theory needs sp3d2 hybridization with the d-orbitals

of S having high energy.
MO theory; 10 MO's from 10 AO's

(4 valence orbitals of S + 6 2p-orbitals of F pointing toward S)
SF6; (1a1)2(1t1)6e4; 8 electrons in bonding orbitals
4 electrons in nonbonding orbitals
⇒ 4 bonding pairs for 6 S–F bonds
⇒ Bond order of S–F = 2

3
Colors of vegetation
HOMO; Highest Occupied Molecular Orbital
LUMO; Lowest Unoccupied Molecular Orbital
Delocalized for conjugated
double bonds (–C=C–C=C–C=C–)
⇒ Electrons-in-a-large
-one-dimensional-box Fig 1.26
⇒ Very close energy levels
⇒ Small HOMO-LUMO gap
⇒ Visible photons can excite electrons

across the gap. ⇒ Colors!
Quiz: Carrot color from b-carotene (C40H56),

tomato color from lycopene (C40H58)?
64

IMPACT ON MATERIALS: ELECTRONIC General Chemistry I (2022) Lecture by B. H. Hong
CONDUCTION IN SOLIDS
Molecular orbitals spread over the entire solid as

a huge molecule.
Electronic conductor; metals and semiconductors,

delocalized electrons as electric current carriers
Metallic conductor;
electric conductivity decreases with temperature Fig 3.43
N (~NA) MO's from N AO's for N electrons

1) Nearly continuous band of energy levels
Enormous N value and large "box"
⇒ Easy to excite electrons into the conduction band where

electrons move freely
2) N electrons occupying ½N bonding MO's

(almost) Zero HOMO-LUMO gap
⇒ High conductivity decreasing with T due to increase
collisions with the vibrating atoms
Insulator; no conductivity
Semiconductor; electric conductivity increases with temperature
Superconductor; zero resistance Box 5.2

3.14 Semiconductors
pn-Junction diodes

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General Chemistry I (2022) Lecture by B. H.

Chapter 03. MOLECULAR SHAPE AND STRUCTURE

Chapter 03. MOLECULAR SHAPE AND STRUCTURE

Chapter 03. MOLECULAR SHAPE AND STRUCTURE

Chapter 03. MOLECULAR SHAPE AND STRUCTURE

Chapter 03. MOLECULAR SHAPE AND STRUCTURE

Chapter 03. MOLECULAR SHAPE AND STRUCTURE

Key Ideas Simple: Electrostatic repulsion between electron pairs

Goal Molecular shape ⇒ Chemical properties

THE VSEPR MODEL

Chapter 03. MOLECULAR SHAPE AND STRUCTURE

MOLECULAR ORBITAL THEORY

THE VSEPR MODEL

Sophisticated quantum mechanical calculations are needed

⇒ Computer-aided "rational drug design"

1) Identification of key enzymes

2) Molecular structure determination

3) Computer-aided design of molecules

3.1 The Basic VSEPR Model

Rule 1: Electron pairs move as far apart as possible.

Rule 2: (Almost) No distinction between single and

3.1 The Basic VSEPR Model

3.1 The Basic VSEPR Model

Ethene (ethylene; C2H4)

The double bond repels more than

3.2 Molecules with Lone Pairs on the Central Atom

Rule 3: Only the positions of atoms are considered when

Ex 3.2 NF3; trigonal pyramidal

Rule 4: For a given angle,

3.2 Molecules with Lone Pairs on the Central Atom

Distortions in NH3, H2O, CH3Cl

Cl is more electronegative than H;

3.2 Molecules with Lone Pairs on the Central Atom

3.2 Molecules with Lone Pairs on the Central Atom

3.2 Molecules with Lone Pairs on the Central Atom

3.2 Molecules with Lone Pairs on the Central Atom

3.3 Polar Molecules

Nonpolar molecule; zero net electric dipole moment

Homonuclear diatomic molecules

Polyatomic molecules with symmetry;

Polar molecule; nonzero electric dipole moment

Lewis model of the chemical bond; localized electron model

Quantum mechanical description of the distribution of electrons in

Valence electrons are localized either between pairs of

1) Hybridization of atomic valence orbitals with proper

2) Placing valence electrons in the hybridized orbitals

3.4 Sigma and Pi Bonds

2) A is formed as two electrons (↑↓) fill the .

; cylindrically symmetrical with no nodal planes

3.4 Sigma and Pi Bonds

3.4 Sigma and Pi Bonds

3.4 Sigma and Pi Bonds

3.5 Electron Promotion and the Hybridization of Orbitals

N, O, and F cannot use promotion to increase valency

Boron, [He]2s22p1, typically forms three bonds

3.5 Electron Promotion and the Hybridization of Orbitals

4 sp3 hybrid orbitals are pointing toward the corners

3.5 Electron Promotion and the Hybridization of Orbitals

Figs 3.13 Figs 3.16c

3.5 Electron Promotion and the Hybridization of Orbitals

3.5 Electron Promotion and the Hybridization of Orbitals

NH3; tetrahedral electron-pair arrangement