Chapter 9

Molecular Geometry and

Bonding Theories

9.1 Molecular Shapes

9.2 The VSEPR Model
9.3 Molecular Shape and Molecular Polarity
9.4 Covalent Bonding and Orbital Overlap
9.5 Hybrid Orbitals
9.6 Multiple Bonds
9.7 Molecular Orbitals
9.8 Bonding in Period 2 Diatomic Molecules
Lecture Goal
• Developing a sense of the shapes of a molecule and
how the shapes are governed by chemical bonds
▪ Various bond types between atoms

▪ The orbital that is participating in bonding

• Connecting 2-D Lewis structure and 3-D molecular shape

• Understanding new concept

▪ Hybrid Orbital and Molecular Orbital

2
9.1 Molecular Shapes

• In Chapter 8, we used Lewis structures to account for the

formulas of covalent compounds
▪ Carbon tetrachloride (CCl4)

▪ In the Lewis structure, all component atoms

are drawn in the same plane

3
9.1 Molecular Shapes

• The shape and size of CCl4

▪ The molecules is tetrahedral (사면체) with bond angle of 109.5º

▪ The C – Cl bond lengths are 1.78 Å (178 pm)

Figure 9.1 Tetrahedral shape of CCl4.

4
9.1 Molecular Shapes

• The shape of molecule of ABn

▪ Single central atom, A, bonded to two or more atom, B

➢ AB2 = CO2, SO2, H2O, …

➢ AB3 = SO3, NH3, ClF3, …

▪ For a molecule of ABn, the number of possible molecule shape

depends on the value of “n”

Figure 9.2 Shapes of AB2 and AB3 molecules. 5

9.1 Molecular Shapes

• What determines the shape of a molecule?

▪ The electron pairs repel each other; whether they are bonding or
nonbonding

▪ The electron pairs are placed as far as possible from each other,
we can predict the shape of the molecule

➢ Each shape, or bond angle,

allows the maximum separation
of outer atoms (B)

6
Figure 9.3 Shapes allowing maximum distance between B atoms in ABn molecules.
9.1 Molecular Shapes

• What determines the shape of a molecule?

▪ Some molecules have shapes other than those shown in Fig. 9.3,
but we can derive the shape of those molecules

Figure 9.4 Derivates of the tetrahedral molecular shape. 7

9.2 The VSEPR Model

• Valence-shell electron-pair repulsion (VSEPR) model

▪ When a central atom is a representative element (one from the s
block or p block of the periodic table), we can use the VSEPR
model to predict the shape of molecules

▪ The model is based on the idea that electron domains are

negatively charged and therefore repel one another

▪ The optimum arrangement of a given number of electron domains

is the one that minimizes the repulsions among them

8
9.2 The VSEPR Model

• Optimum geometry: Imagine

the two identical balloons
▪ Two identical balloons are tied together
at their ends; they try to get out of
each other’s way

▪ Add a third balloon; they orient themselves

toward the vertices of an equilateral triangle
(정삼각형)

▪ Adding a fourth one; they adopt tetrahedral

shape (사면체)
Figure 9.5 A balloon analogy
for electron domains. 9
9.2 The VSEPR Model

• Electron domains
▪ A bonding pair of electrons defines a region in which the electrons
are most likely to be found

▪ In a double or triple bond, all electrons shared between those two

atoms are on the same side of the central atom; therefore, they
count as one electron domain

▪ A nonbonding pair (or lone pair) of electrons

also defines an electron domain located
principally on one atom

The central atom in this molecule, A, has four electron domains

(or coordination number or steric number =4 ) 10
9.2 The VSEPR Model

• Electron domains
▪ Ammonia (NH3) has four electron domains around the central N
atom

▪ Ozone (O3) has three electron domains around the central O atom

11
9.2 The VSEPR Model

• The arrangement of electron domains around the central

atom of an ABn molecule or ion is called “its electron-
domain geometry”
▪ The optimum geometry will be determined by the number of
electron domains (See Table 9.1)

▪ All one must do is to count the number of electron domains in

the Lewis structure

• Molecular geometry is the arrangement of only the atoms

in a molecule or ion
▪ any nonbonding pairs in the molecule are not part of the
description of the molecular gemoetry
12
9.2 The VSEPR Model

13
9.2 The VSEPR Model

14
Applying the VSEPR Model to Determine Molecular Shapes

• In determining the shape of molecule,

▪ We first use the VSEPR model to predict the electron-domain
geometry

▪ When there are no nonbonding electron domains, the molecular

geometry is identical to the electron-domain geometry

▪ When one or more domains involve nonbonding pairs of electrons,

the molecular geometry involves only electron domains due to bonds

15
Applying the VSEPR Model to Determine Molecular Shapes

• How to predict the shapes of molecules and ions using the

VSEPR model
1. Draw the Lewis structure and count the number of electron domains
around the central atom

2. Determine the electron-domain geometry by arranging the electron

domains about the central atom so that the repulsions among the
are minimized (Table 9.1)

3. Use the arrangement of the bonded atoms to determine the

molecular geometry

16
Applying the VSEPR Model to Determine Molecular Shapes

• Molecular geometries
▪ The electron-domain geometry is often not the shape of the molecule

▪ The molecular geometry is defined by the positions of only the atoms

in the molecules; the nonbonding pairs is not considered

17
Applying the VSEPR Model to Determine Molecular Shapes

• Ammonia (NH3)
▪ Lewis structure : 3 bonds and one nonbonding pair around N atom
→ 4 electron domains (Electron-domain geometry : tetrahedral)

▪ The molecular geometry is defined by only 3 N – H bond domains

→ Molecular geometry : trigonal pyramidal (bond angle 109.5º)

Figure 9.6 Determining the molecular geometry of NH3. 18

Applying the VSEPR Model to Determine Molecular Shapes

• Carbon dioxide (CO2)

▪ Lewis structure : 2 double bonds around C atom
→ 2 electron domains (Electron-domain geometry : linear)

▪ There are no nonbonding electron pairs, so the molecular geometry

is equal to the electron-domain geometry, linear (bond angle 180º)

180º

19
Applying the VSEPR Model to Determine Molecular Shapes

• Linear electron domain (n = 2)

▪ In the linear domain, there is only one molecular geometry is ‘Linear’

▪ NOTE: If there are only two atoms in the molecule, the molecule will
be linear no matter what the electron domain is

20
Applying the VSEPR Model to Determine Molecular Shapes

• Trigonal planar electron domain (n = 3)

▪ If all the electron domains are bonding, the molecular geometry is
‘Trigonal planar’

▪ If a domain is a nonbonding pair, the molecular geometry is ‘Bent’

21
Applying the VSEPR Model to Determine Molecular Shapes

• Tetrahedral electron domain (n = 4)

▪ If all the electron domains are bonding, the molecular geometry is
‘Tetrahedral’

▪ If one is a nonbonding pair, the molecular geometry is ‘Trigonal

pyramidal’

▪ If there are two nonbonding pairs, the molecular geometry is ‘Bent’

22
Applying the VSEPR Model to Determine Molecular Shapes

• Tetrahedral electron domain (n = 4)

23
Effect of Nonbonding Electrons and Multiple Bonds on Bond Angles

• Bond angle
▪ When molecules have the identical electron-domains, the molecules
have an ideal geometries summarized in Table 9.2

▪ Nonbonding electrons and multiple bonds cause slight changes in

their molecular geometries

24
Effect of Nonbonding Electrons and Multiple Bonds on Bond Angles

• Effect of nonbonding electrons on bond angle

▪ CH4, NH3, and H2O have a tetrahedral electron-domain geometry

➢ Bond angles decrease as the number of nonbonding electron pairs

increase

25
Effect of Nonbonding Electrons and Multiple Bonds on Bond Angles

• Effect of nonbonding electrons on bond angle

▪ Electron domains for nonbonding pairs exert greater repulsive forces
on adjacent electron domains and tend to compress bond angles

➢ A bonding pair is attractive by both nuclei of the bonded atoms, but a

nonbonding pair is attracted by only one nucleus

➢ A nonbonding pair experiences less nuclear attraction, so its electron

domain is spread out more in space than a bonding pair

Figure 9.7 Relative volume occupied by

bonding and nonbonding electron domains.
26
Effect of Nonbonding Electrons and Multiple Bonds on Bond Angles

• Effect of multiple bonds on bond angle

▪ Multiple bonds contain a higher electronic-charge density than single
bonds, the multiple bonds represent enlarged electron domains

➢ Electron domains for multiple bonds exert a greater repulsive force on

adjacent electron domains than do electron domains for single bonds

Phosgene (Cl2CO)

27
Molecules with Expanded Valence Shells

• Some atoms from period 3 and beyond can

▪ break the octet rule and

▪ be surrounded by more than 4 electron pairs, or have more than 4

electron domains

• The result is two more possible electron-domain geometries:

▪ If n = 5, trigonal bipyramidal (삼각 쌍뿔)

▪ If n = 6, octahedral (팔면체)

28
Molecules with Expanded Valence Shells

• Trigonal bipyramidal (n = 5)
▪ The most stable electron-domain geometry is the trigonal bipyramidal
(sharing a base)

▪ 2 domains point toward axial position (축방향), and 3 domains toward

equatorial position (적도방향)
90º
▪ An equatorial domain experiences less
repulsion than an axial domain
120º
▪ Nonbonding domains always occupy
the equatorial positions
in a trigonal bipyramid. Figure 9.8 In a trigonal-bipyramidal
geometry, there are two types of
positions for the outer atoms.29
Molecules with Expanded Valence Shells

• Trigonal bipyramidal (n = 5)
▪ If all the electron domains are bonding, the molecular geometry is
‘Trigonal bipyramidal’

▪ If one is a nonbonding pair, the molecular geometry is ‘Seesaw’

▪ If there are two nonbonding pairs, the molecular geometry is

‘T-shaped’

▪ If there are three nonbonding pairs, the molecular geometry is

‘Linear’

30
Molecules with Expanded Valence Shells

• Trigonal bipyramidal (n = 5)

31
Molecules with Expanded Valence Shells

• Octahedral (n = 6)
▪ The most stable electron-domain geometry is the octahedron

▪ The atom is at the center of the octahedron with the 6 electron

domains point toward each vertices, with all bond angles are 90º

▪ If all the electron domains are bonding, the molecular geometry is

‘Octahedral’

▪ If one is a nonbonding pair, the molecular geometry is ‘Square

pyramidal’

▪ If there are two nonbonding pairs, the molecular geometry is

‘Square planar’
32
Molecules with Expanded Valence Shells

• Octahedral (n = 6)

33
Molecules with Expanded Valence Shells

Sample Exercise 9.2 [Page 393]

▪ Use the VSEPR model to predict the molecular geometry of (a) SF4,
(b) IF5.

(a) SF4
Lewis structure Electron-domain geometry is trigonal bipyramidal
An electron-domain in the equatorial position is
a nonbonding pair

5 electron domains
(4 bonding pairs and 1 nonbonding pair) 34
Molecules with Expanded Valence Shells

Sample Exercise 9.2 [Page 393]

▪ Use the VSEPR model to predict the molecular geometry of (a) SF4,
(b) IF5.

(b) IF5
Lewis structure Electron-domain geometry is octahedral
We can put the nonbonding domain at any of the six
vertices of the octahedron
Smaller than 90º
(82º)

6 electron domains
(5 bonding pairs and 1 nonbonding pair) 35
Shapes of Larger Molecules

• The VSEPR model can be extended to more complex

molecules
▪ Electron-domain geometries of each atoms in acetic acid (CH3COOH)

36
 Shapes of Larger Molecules

• The VSEPR model can be extended to more complex

molecules
▪ Molecular geometries of each atoms in acetic acid (CH3COOH)

Tetrahedral Bent
< 120º

< 109.5º
Trigonal planar

Figure 9.9 The electron-domain and molecular geometries around the three central
37
atoms of acetic acid, CH3COOH.
Shapes of Larger Molecules

Sample Exercise 9.3 [Page 395]

▪ Eyedrops for dry eyes usually contain a water-soluble polymer
poly(vinyl alcohol), which is based on the unstable organic molecule
vinyl alcohol:

Predict the approximate values for the H – O – C and O – C – C bond

angles in vinyl alcohol.

38
Shapes of Larger Molecules

Sample Exercise 9.3 [Page 395]

1) H – O – C bond : The central O atom has 4 electron domains
(2 bonding pairs & 2 nonbonding pairs)

Molecular geometry is bent

We expect H – O – C bond angle to be slightly less than 109.5º

2) O – C – C bond : The central C atom has 3 electron domains

(2 single bonding pairs & 1 double bonding pairs)

Molecular geometry is trigonal planar

We expect O – C – C bond angle to be slightly greater than 120º

39
9.3 Molecular Shape and Molecular Polarity

• In Section 8.4, we discuss “the bond polarity and dipole

moment”
▪ Bond polarity is a measure of how equally the electrons in a bond
are shared between the two atoms of the bond

• Just because a molecule has polar bonds does not mean

that the entire molecule will be polar

40
9.3 Molecular Shape and Molecular Polarity

• Carbon dioxide (CO2)

▪ Each C = O bond is polar

▪ In linear CO2 molecule, two identical C = O bonds (equal in

magnitude, opposite in direction) “cancel” each other

• Water (H2O)
▪ Each H – O bond is polar, and the two H – O bonds are equal in
magnitude

▪ The molecule is bent, so the bond dipoles do not directly oppose

each other and therefore do not cancel

41
 9.3 Molecular Shape and Molecular Polarity

Figure 9.10 CO2, a nonpolar molecule, and H2O, a polar molecule.

42
 9.3 Molecular Shape and Molecular Polarity

• Fig. 9.11 shows some examples of polar and nonpolar

molecules, all with polar bonds
▪ The molecules in which the central atom is symmetrically
surrounded by identical atoms (BF3 and CCl4) are nonpolar

Figure 9.11 Polar and nonpolar molecules containing polar bonds.

The numbers are electronegativity values. 43
9.3 Molecular Shape and Molecular Polarity

Sample Exercise 9.4 [Page 397]

▪ Predict whether these molecules are polar or nonpolar: (a) BrCl,
(b) SO2, (c) SF6.

(a) BrCl

Cl is more electronegative than Br

(b) SO2

O is more electronegative than S

Lewis structure of SO2

44
9.3 Molecular Shape and Molecular Polarity

Sample Exercise 9.4 [Page 397]

▪ Predict whether these molecules are polar or nonpolar: (a) BrCl,
(b) SO2, (c) SF6.

(c) SF6

F is more electronegative than S

Lewis structure of SF6

The 6 S – F bonds are arranged octahedrally

around the central S

Because the molecular geometry is symmetrical,

the bond dipoles cancel, and the molecular is nonpolar
45
9.4 Covalent Bonding and Orbital Overlap

• Valence-bond theory (원자가 결합 이론)

▪ The marriage of Lewis‘s notion of electron-pair bonds and the idea
of atomic orbitals

➢ In Lewis theory, covalent bonding occurs

when atoms share electrons because
the sharing concentrates electron density
between the nuclei

➢ The overlap of orbitals allows

two electrons of opposite spin to share
the space between the nuclei,
forming a covalent bond Figure 9.12 Covalent bonds in
H2, HCl, and Cl2 result from
H = 1s1 Cl = [Ne]3s23p5 overlap of atomic orbitals.
46
9.4 Covalent Bonding and Orbital Overlap

• Optimum distance between the two nuclei in covalent bond

▪ Increase in orbital overlap brings electrons and nuclei closer
together, decreasing repulsive force between electrons

▪ If atoms get too close,

the inter-nuclear repulsion greatly
raises the energy

▪ The internuclear distance

at the minimum of the
potential energy corresponds to
the bond length Figure 9.13 Formation of the H2 molecule as
atomic orbital overlap.
47
9.5 Hybrid Orbitals

• How can we reconcile the notion that covalent bonds are

formed from overlap of atomic orbitals with the molecular
geometries that come from the VSEPR model?
▪ We assume that the atomic orbitals on an atom mix to form new
orbitals called “hybrid orbitals”

▪ Hybridization is the mathematical process of mixing atomic

orbitals

▪ The number of hybrid orbitals on an atom equals the number of

atomic orbitals that are mixed

48
𝑠𝑝 Hybrid Orbitals

• Consider BeF2 molecule

▪ In its ground electronic state, Be cannot bond with the F atoms

▪ If absorbs the small amount of energy needed to promote an

electron from the 2s to the 2p orbital, it can form two bonds

49
𝑠𝑝 Hybrid Orbitals

• Consider BeF2 molecule

▪ However, the two bonds would not be identical because each
bond is formed by either 2s orbital or 2p orbital, they are not
identical

▪ We solve this dilemma by “mixing” the 2s orbital with one 2p orbital

to generate two new orbitals (identical in shape, but their large
lobes point in opposite directions)

Figure 9.14 Formation of sp hybrid orbitals.

50
𝑠𝑝 Hybrid Orbitals

• Consider BeF2 molecule

▪ sp hybrid orbital is hybridized by one s and one p orbital

▪ A linear arrangement of BeF2 implies sp hybridization

▪ The electrons in the sp hybrid orbitals can form bonds with the two
F atoms

Figure 9.15 Formation of two equivalent Be – F bonds in BeF2.

51
𝑠𝑝2 and 𝑠𝑝3 Hybrid Orbitals

• Consider BF3 molecule

▪ Three equivalent 𝑠𝑝2 hybrid orbitals are hybridized by one 2s and
two of the 2p orbitals

▪ They form equivalent bonds with the three F atoms, leading to the
trigonal-planar molecular geometry of BF3

Figure 9.16 Formation of 𝒔𝒑𝟐 hybrid orbitals.

52
𝑠𝑝2 and 𝑠𝑝3 Hybrid Orbitals

• Consider CH4 molecule

▪ Four equivalent 𝑠𝑝3 hybrid orbitals are hybridized by one 2s and all
three 2p orbitals

▪ They form four equivalent two-electron bonds by overlap with the

atomic orbitals of another atom, such as H

53
𝑠𝑝2 and 𝑠𝑝3 Hybrid Orbitals

• Consider CH4 molecule

Figure 9.17 Formation of 𝒔𝒑𝟑 hybrid orbitals.

54
𝑠𝑝2 and 𝑠𝑝3 Hybrid Orbitals

• In H2O molecule,
▪ Four 𝑠𝑝3 hybrid orbitals are formed, and two hybrid orbitals contain
nonbonding pairs of electrons, and the others form bonds with the
H atom

Figure 9.18 Hybrid orbital description of H2O.

55
Hypervalent Molecules

• Elements of period 3 and beyond

▪ The VSEPR model works well to predict the geometries of
hypervalent molecules such as PCl5, SF6, or BrF5

▪ However, the hybrid orbitals should not be used for the

hypervalent molecules

56
Hybrid Orbital Summary

• How to describe the hybrid orbitals used by an atom in

bonding
1. Draw the Lewis structure for the molecule or ion

2. Use the VSEPR model to determine the electron-domain

geometry around the central atom

3. Specify the hybrid orbitals needed to accommodate the electron

pairs based on their geometric arrangement

57
Hybrid Orbital Summary

58
Hybrid Orbital Summary

• How to describe the hybrid orbitals in NH3

Figure 9.19 Hybrid orbital description of bonding in NH3.

59
Hybrid Orbital Summary

Sample Exercise 9.5 [Page 405]

▪ Describe the orbital hybridization around the central atom in NH2-.

The Lewis structure is

Four electron domains around N, the electron-domain geometry is

‘tetrahedral’

The hybridization that gives a tetrahedral is 𝒔𝒑𝟑 hybrid orbital.

60
9.6 Multiple Bonds
• Valence-Bond Theory
▪ Hybridization is a major player in this approach to bonding

𝑠𝑝, 𝑠𝑝2 , 𝑠𝑝3

▪ There are two ways (hybrid) orbitals can overlap to form bonds
between atoms

Internuclear axis (or bond axis) is

the imaginary straight line that
connects the nuclei of atoms bonded
to each other in a molecule.

61
9.6 Multiple Bonds
• Sigma (s) bond
▪ In the covalent bonds, the electron density is concentrated along
the line connecting the nuclei (the internuclear axis)

▪ Head-to-head overlap

62
Figure 9.20 Comparison of s and p bonds.
9.6 Multiple Bonds
• Pi (p) bond
▪ Overlap between two p orbitals oriented perpendicularly to the
internuclear axis

▪ The sideways overlap (Side-to-side overlap)

▪ p bonds are generally weaker than s bonds

63
Figure 9.20 Comparison of s and p bonds.
9.6 Multiple Bonds
• Multiple bonds
▪ Single bonds are s bonds

▪ Double bonds consist of one s bond and one p bond

▪ Triple bonds consist of one s bond and two p bonds

64
9.6 Multiple Bonds
• Double bond
▪ In ethylene (C2H4), there are three bond around each carbon (the
angles are about 120º)

▪ Each C atom uses 𝑠𝑝2 hybrid orbitals to form s bonds with the other
carbon and with two H atoms

▪ One electron in each C remains in the unhybridized 2p orbital,

directed perpendicular to the plane that contains the three 𝑠𝑝2
hybrid orbitals

65
Figure 9.21 Trigonal-planar molecular geometry of ethylene.
9.6 Multiple Bonds
• Double bond
▪ One 𝑠𝑝2 orbital in each C atom
form the C – C s bond

▪ The others 𝑠𝑝2 orbital in C atom

form the C – H s bonds

▪ Unhybridized 2p orbital in
each C atom can overlap
sideways with each other,
electrons in the 2p orbitals form
the C – C p bond

66
9.6 Multiple Bonds
• Triple bond
▪ In acetylene (C2H2), there are two electron domains around each C
atom (geometries are linear)

▪ Each C atom uses 𝑠𝑝 hybrid orbitals to form s bonds with the other
carbon and with a H atom

▪ Each C has two unhybridized 2𝑝 orbitals at right angles to each

other and to the axis of the 𝑠𝑝 hybrid set

▪ These 𝑝 orbitals overlap to form a pair of p bonds

67
9.6 Multiple Bonds
• Triple bond
▪ The triple bond in acetylene,
C2H2, consists of
one s bond (𝑠𝑝 – 𝑠𝑝) and
two p bonds (2𝑝 – 2𝑝)

Figure 9.23 Hybrid orbital bonding in acetylene,

C2H2. 68
9.6 Multiple Bonds
Sample Exercise 9.6 [Page 408]
▪ Formaldehyde has the Lewis structure

Describe how the bonds in formaldehyde are formed in terms of

overlaps of hybrid and unhybridized orbitals.

The C and O atoms have three electron-domains, which suggests

trigonal-planar geometries with bond angles of about 120º

Each atom has three sp2 hybrid orbitals and an unhybridized 2p orbital

Formaldehyde has two C – H s bonds,

one C – O s bond
and one C – O p bond

Figure 9.24 Formation of s and p bonds in formaldehyde,

69 H2CO.
Resonance Structures, Delocalization, and p Bonding

• Localization
▪ s and p electrons are associated totally with the two atoms that form
the bond

▪ However, in many molecules, we cannot adequately describe the

bonding as being entirely localized

➢ Molecules that have two or more resonance structures involving p

bonds

70
Resonance Structures, Delocalization, and p Bonding

• Benzene (C6H6)
▪ Two resonance structures and total of 30 valence electrons

▪ Each C is surrounded by three atoms at 120º angles, 𝑠𝑝2 hybrid set

▪ 6 localized C – C s bonds and 6 localized C – H s bonds (24 e-)

▪ Electrons in unhybridized p orbitals form three p bonds (6 e-)

Figure 9.25 s and p bond networks in benzene, C6H6. 71

Resonance Structures, Delocalization, and p Bonding

• Benzene (C6H6)
▪ There are two equivalent ways to make these p bonds (resonance)

▪ The 6 C – C bond lengths are 140 pm, between single bond (154
pm) and double bond (134 pm)

▪ Benzene has a six-electron p system delocalized among the 6 C

atoms → Delocalization system gives C6H6 a special stability

Figure 9.26 Delocalized p bonds in benzene, C6H6.

72
 Resonance Structures, Delocalization, and p Bonding

Sample Exercise 9.7 [Page 410]

▪ Describe the bonding in the nitrate ion, NO3-. Does this ion have
delocalized p bonds?
In each N and O atom,
Electron-domain geometry
: trigonal-planar
3 𝑠𝑝2 hybrid and an unhybridized 𝑝 orbital

3 N – O s bonds Figure 9.27 Localized and delocalized representations of

73
6 nonbonding electron pairs the six-electron p system in NO3-.
General Conclusions about s and p Bonding

• Every pair of bonded atoms shares one or more pairs of

electrons

• s bonds are localized in the region between two bonded

atoms

• When atoms share more than one pair of electrons, one

pair is used to form s bond; the others form p bonds

• Molecules can have p systems that extend over more than

two bonded atom → “delocalized” p systems

74
9.7 Molecular Orbitals

• In Chapter 6,
▪ Electrons in atoms can be described by wave functions, called as
atomic orbitals

• In a molecular orbital theory,

▪ Electrons in molecules can be described by specific wave
functions, each of which is called a molecular orbital (MO)

▪ MOs have many of the same characteristics as atomic orbitals,

however, the Mos are associated with an entire molecule, not with
a single atom

75
Molecular Orbitals of the Hydrogen Molecule

• In H2 molecule,
▪ Overlap of 1s orbitals of two H atoms to form H2 produces two MOs

➢ Bonding molecular orbital (s1s)

: electron density is concentrated in the region between the nuclei

➢ Antibonding molecular orbital (s*1s)

: electron density on opposite
sides of the two nuclei and
has a plane in the region,
where the electron density
is zero (nodal plane)

Figure 9.31 The two molecular orbitals of H2,

76
one a bonding MO and one an antibonding MO.
Molecular Orbitals of the Hydrogen Molecule

• In H2 molecule,
▪ Energy level of bonding and antibonding MO

➢ An electron in bonding MO is attracted to both nuclei, the electron is

more stable (it has lower energy)

➢ An electron in antibonding MO H2 : 𝝈𝟏𝒔 𝟐

is repelled from the bonding region,
the electron is less stable
(it has higher energy)

➢ Each MO can accommodate

two electrons with their spins paired

Figure 9.32 Energy-level diagram and electron

77
configuration for H2.
Bond Order (결합차수)

• Bond order determines the stability of a covalent bond

1
▪ Bond order = (# of bonding electrons - # of antibonding electrons)
2

➢ A bond order of 1, 2, and 3 represents a single bond, double bond, and

triple bond, respectively
1
✓ H2 (𝜎1𝑠 2 ) = 2−0 =1
2

∗ 2 1
✓ He2 (𝜎1𝑠 2 𝜎1𝑠 )= 2 − 2 = 0, it means that no bond exists
2

78
Bond Order (결합차수)

• Bond order determines the stability of a covalent bond

Figure 9.32 Energy-level diagram and Figure 9.33 Energy-level diagram and
electron configuration for H2. electron configuration for He2.
※ Molecular orbital theory correctly predicts that hydrogen forms diatomic
79
molecules, but helium does not.
Bond Order (결합차수)

Sample Exercise 9.8 [Page 415]

▪ What is the bond order of the He2+ ion? Would you expect this ion to
be stable relative to the separated He atom and He+ ion?

The energy-level diagram for the He2+ ion

1 1
Bond order = 2−1 =
2 2

Bond order > 0

Therefore, the He2+ ion to be stable
relative to the separated He and He+

Figure 9.34 Energy-level diagram

80
for the He2+ ion.
9.8 Bonding in Period 2 Diatomic Molecules

• Interaction of valence 2s and 2p orbitals to form MOs

1. # of MOs formed equals # of atomic orbitals combined

2. Atomic orbitals combine most effectively with other atomic orbitals

of similar energy

3. As the overlap increases, the energy of the bonding MO and

antibonding MO is lowered and raised, respectively

4. Each MO can accommodate, at most, two electrons, with their

spins paired (Pauli exclusion principle)

5. When Mos of the same energy are populated, one electron enters
each orbital before spin pairing occurs (Hund’s rule)
81
Molecular Orbitals for Li2 and Be2

• MO from 2s atomic orbitals

▪ 1s orbital on one atom interacts only 1s orbital on the other atom
and 2s orbital interacts only with each other

▪ 4 atomic orbitals produces 4 MOs

▪ Because 2s orbitals larger than 1s orbitals, the 2s orbitals overlap

more effectively

▪ The 1s orbitals are much lower in energy than 2s orbitals; therefore,

∗
the energy of the 𝜎1𝑠 is much lower than the energy of the 𝜎2𝑠

▪ The electrons are filled according to the energy-level of MOs

82
Molecular Orbitals for Li2 and Be2

• Li2
∗ 2
▪ 6 electrons (Electron configuration is 𝜎1𝑠 2 𝜎1𝑠 𝜎2𝑠 2 )

1
▪ Bond order = 4 − 2 = 1, indicates a Li – Li single bond
2

• Be2
▪ 8 electrons (Electron configuration
∗2 ∗ 2
is 𝜎1𝑠 2 𝜎1𝑠 𝜎2𝑠 2 𝜎2𝑠

1
▪ Bond order = 4 − 4 = 0,
2
therefore, Be2 does not exist
Figure 9.35 Energy-level diagram
83
for the Li2 molecule.
Molecular Orbitals from 𝟐𝒑 Atomic Orbitals

• MO from 2𝑝 atomic orbitals

▪ Three type of 2p atomic orbitals (2𝑝𝑥 , 2𝑝𝑦, and 2𝑝𝑧)

▪ One type of 2p atomic orbital lies along the internuclear axis, these
∗
orbitals face each other head-to-head and form 𝜎2𝑝 and 𝜎2𝑝

▪ The other 2p atomic orbitals overlap sideways and form two 𝜋2𝑝
∗
and 𝜋2𝑝

➢ These two p (anti) bonding Mos have the same energy (degenerate)

84
 Molecular Orbitals from 𝟐𝒑 Atomic Orbitals

Figure 9.41 Energy-level diagram for Mos of

period 2 homonuclear diatomic molecule.

Figure 9.36 Contour representations of the molecular orbitals formed by 𝟐𝒑 orbitals. 85

Electron Configurations for B2 through Ne2

• MO from valence 2s and 2p atomic orbitals

▪ The 2𝑠 atomic orbitals are substantially lower in energy than 2𝑝
∗
atomic orbitals : 𝜎2𝑠 < 𝜎2𝑠 < 𝜎2𝑝 (the lowest MO derived from the 2𝑝)

▪ The overlap of the two 2𝑝𝑧 orbitals (along internuclear axis) is

greater than that of the two 2𝑝𝑥 or 2𝑝𝑦 orbitals
∗ ∗
: 𝜎2𝑝 < 𝜋2𝑝 and 𝜎2𝑝 > 𝜋2𝑝
∗
▪ Both the 𝜋2𝑝 and 𝜋2𝑝 Mos are doubly degenerate

86
Electron Configurations for B2 through Ne2

• 2𝑠 – 2𝑝 interaction
▪ Interaction between the 2s orbital on one atom and the 2p orbitals
on the other can alter the energetic ordering of the MOs

Figure 9.42 The effect of interactions between 𝟐𝒔 and 𝟐𝒑 atomic orbitals. 87

Electron Configurations for B2 through Ne2

• Electron configuration for B2

▪ Valence electrons are filled in a given MO starting from the lowest
energy MO

▪ A B2 molecule has six valence electrons

∗
➢ Four of them fill the 𝜎2𝑠 and 𝜎2𝑠 MOs → No net bonding

➢ The fifth electron goes in one 𝜋2𝑝 MO and the sixth electron goes in
the other 𝜋2𝑝 MO, with the two electrons having the same spin

1
➢ Bond order = 2 4 − 2 = 1

88
 Electron Configurations for B2 through Ne2

Figure 9.43 Molecular orbital electron configurations and some experimental data for
period 2 diatomic molecules.
89
Electron Configurations for B2 through Ne2

• Diamagnetism
▪ Diamagnetism (반자성) : Substances with no unpaired electrons,
these substances are weakly repelled by a magnetic field

▪ Paramagnetism (상자성) : Substances with unpaired electrons,

these substances are attracted by a magnetic field

90
Figure 9.44 Determining the magnetic properties of a sample.
Electron Configurations for B2 through Ne2

• Bond stability according to bond order

▪ As bond order increases, bond distances decrease, and bond
enthalpies increase

➢ N2, whose bond order 3, has a short bond distance and a large bond
enthalpy

➢ N2 molecule does not react readily with other substances to form N

compounds

➢ That molecules with the same bond orders do not have the same bond
lengths and enthalpies

91
Electron Configurations for B2 through Ne2

• Paramagnetism of O2
∗
▪ O2 molecule has two unpaired electrons in 𝜋2𝑝

➢ The molecule is paramagnetic, a detail not discernible in the Lewis

structure

➢ Liquid oxygen “sticks” to the poles of magnet

Figure 9.45 Paramagnetism of O

922.
Electron Configurations for B2 through Ne2

Sample Exercise 9.9 [Page 423]

▪ For the O2+ ion predict (a) number of unpaired electrons, (b) bond
order, (c) bond enthalpy and bond length.

O2+ ion has 11 valence electrons, one fewer than O2.

(a) one unpaired electron

1 1
(b) Bond order = 2 8 − 3 = 2 2

(c) Bond enthalpy and length are midway

between those for O2 and N2,
approximately 700 kJ/mol and 115 pm
93
O2 O2+
Heteronuclear Diatomic Molecules

• Molecular orbital theory can be extended to heteronuclear

diatomic molecules

• Nitric oxide (NO)

▪ Lewis structure

▪ It has 11 valence electrons

▪ Experimental bond length of NO, 115 pm, suggests a bond order

greater than 2

94
Heteronuclear Diatomic Molecules

• If the atoms do not differ too greatly in electronegativities

▪ 2s and 2p atomic orbitals of O (more electronegative) are slightly
lower than those of N (less electronegative)

▪ An MO in a heteronuclear diatomic molecule has a greater

contribution from the atomic orbital to which it is closer in energy

▪ The 11 valence electrons goes in the MO in order increasing energy

1 1
➢ Bond order = 2 8 − 3 = 2 2

95
96
 Homework : Chap 9

• Exercise [Page 428 ~ ]

▪ 16, 26, 42, 46, 52, 58, 60, 72, 87, 91

▪ Due : ~ 5/22 (Mon) 09:00

▪ Blackboard system – 과제 및 시험

97