Chapter 5 CHEM 241

Winter 2021
© Drs. XO, PHB, RN, AJH, & CWR Molecular Orbital (M.O.) Theory Ch.5b − Slide.1

5.3 Heteronuclear Diatomic Molecules

5.3.1 Polar Bonds
5.3.2 Ionic Compounds and Molecular Orbitals

5.4 Molecular Orbitals for Larger Molecules: Polyatomics

BeH2 – an example involving non-classical bonding
 CHEM 241
Heteronuclear Diatomic Molecules & Ions Winter 2021
© Drs. XO, PHB, RN, AJH, & CWR Ch.5b − Slide.2
Orbital Energy (eV)

Remember, if two combining

orbitals do not have the same
energy, the greater the
difference, the more closely the
Atomic # resulting molecular orbitals
resemble the parent orbitals.
Across a period:
• atomic orbital Es decrease steadily TRICK: use your fingers…
(as Zeff ↑  e- attraction to nucleus ↑) p p p
p
• E gap between s & p orbitals increases s
s s
(↑ penetration of s  amplifies 1st effect) s
no s-p mixing
Estimated relative Es are used when we draw MO if gap is big significant
diagrams for heteronuclear diatomic molecules. s-p mixing
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MOs for Heterodiatomics - Question Winter 2021
Ch.5b − Slide.3

Molecular orbitals are made from linear combinations of the atomic orbitals
(LCAOs) of the bonded atoms. Remember that orbital energy and size, for
example, are proportional, and that orbitals of similar energy and size
overlap more efficiently with each other. The characteristics of the resulting
MOs – energy, shape, size, location – depend on the contribution (i.e.,
coefficient) of each parent orbital.
When the energies of the combining orbitals are very different, the parent
orbitals contribute unevenly to the MOs:
the lower-energy AO contributes more to the lower-energy MO, and vice versa.

Which statement about the character of the MOs of heterodiatomic

molecules is incorrect?
A. Lower energy MOs have similar energy and location to the more
electronegative atom’s orbitals.
B. Higher energy MOs have similar energy and location to the more 
electronegative atom’s orbitals.
C. Nonbonding MOs have nearly identical energy and location to the
parent atom’s orbitals.
 WHY CARE? Picture rxn with base: CHEM 241

© Drs. XO, PHB, RN, AJH, & CWR

M.O.s for HF • Which orbital do base’s 2 e-s enter?
• What happens to HF B.O.?
Winter 2021
Ch.5b − Slide.4

* This is the MO diagram for HF including

all valence shell atomic orbitals. Note:
- 13.6 eV • The relative levels of the H 1s & F 2p
orbitals reflect the relative Zeff (χ…)
felt by these two atoms’ valences.
(Recall: the higher the E of the HOMO,
the easier it is to ionize the atom.)
• The two F 2p orbitals (called “1π” in
- 18.7 eV molecule) perpendicular to the H-F
bond are not changed, i.e., they are
- 40.2 eV
non-bonding (house lone pairs).
(A.O.s not aimed in a way that leads to
≈ nonbonding
Fig. adapted from: Shriver & Atkins, Freeman
bonding are not used to make MOs.)
• 2σ orbital: somewhat bonding & mainly F 2p in character (…very polar bond).
• 1σ orbital: almost entirely F character. The F 2s & H 1s orbitals are so different in E
that they barely interact (i.e., this is essentially a lone pair on F).
See Miessler Exercise 5.3: F’s 2s treated as truly non-bonding.

Polar covalent bonding: bonding MOs dominated by more electronegative atom.

vs. Ionic bonding: bonding MOs ~entirely from more electronegative atom.
 M.O. notation: always label symmetry, & CHEM 241
Winter 2021
© Drs. XO, PHB, RN, AJH, & CWR some books number them for clarity Ch.5b − Slide.5

HF MOs from Shriver & Atkins: HF MOs from Miessler Exercise 5.3:
• includes contribution from F’s 2s • ignores contribution from F’s 2s orbital entirely
• Notation: by symmetry (σ, π, σ*...) (E too far from H’s 1s, so it is quite reasonable)
numbered in ↑ E by type • Notation: symmetry indicated, but not #d
(#s just make for easier reference)
*

- 13.6 eV

- 18.7 eV

- 40.2 eV

H-F
 Drawing an M.O. diagram (1): CHEM 241
Winter 2021
© Drs. XO, PHB, RN, AJH, & CWR Carbon Monoxide - :C≡O: + Ch.5b − Slide.6

FIRST : THINK ABOUT PARENT ATOMS & OUR EXPECTATIONS OF MOLECULE

1. Draw Lewis structure (define our naïve expectations).
2. Determine relative E of parent atoms’ valence orbitals (all, even if unoccupied).
• homodiatomic: same E valence orbitals for both atoms
• heterodiatomic: higher χ  lower E valence orbitals, & larger s-p gap
3. Draw E levels of parent atoms at far left & far right of MO diagram E scale.

parent molecule parent

C CO O
2p

Orbital Energy (eV)

2s

Note: χO > χC Z
• lower avg 2s-2p E
• larger 2s-2p gap

Fig. adapted from: Shriver & Atkins, Freeman

 Drawing an M.O. diagram (2): CHEM 241
Winter 2021
© Drs. XO, PHB, RN, AJH, & CWR Carbon Monoxide - :C≡O: + Ch.5b − Slide.7

NEXT : OVERLAP ATOMIC ORBITALS TO MAKE MOs (work in pencil here!)

4. Pair symmetry-matched orbitals to yield bonding/antibonding MOs (ignore NBs now)
• s-s  σ + σ∗ (very low E pair of MOs) AND p-p  σ + σ∗ (medium E pair)
p-p  π + π∗ (in between σp-p pair)
5. Atomic orbitals not used (=NBs) stay at original E; slide over to MOs & name as σ/π.

C CO O C CO O
4a. Start
with just
2π∗
σ-overlaps

4b. Add in
π-overlaps 1π

3σ 3σ

Fig. adapted from: Shriver & Atkins, Freeman

 Drawing an M.O. diagram (3): CHEM 241
Winter 2021
© Drs. XO, PHB, RN, AJH, & CWR Carbon Monoxide - :C≡O: + Ch.5b − Slide.8

LAST: CORRECT FOR MIXING & VISUALIZE RESULTING e--DISTRIBUTION

6. Correct for s-p mixing: drop lower E σ/σ∗ very low & raise higher E σ higher than π,
& acknowledge complex parentage (not just pairs now)
7. Add electrons, & identify bonds (between atoms) vs lone pairs (mostly on one atom).
8. Compare to Lewis structure: bond order, bond locations, lone pair locations, etc…

C CO O C CO O

2π∗ 2π∗

correct for 3σ
1π
s-p mixing
1π
3σ + add e-s

Fig. adapted from: Shriver & Atkins, Freeman

 CHEM 241

© Drs. XO, PHB, RN, AJH, & CWR

The Real MOs for CO: - :C≡O: + Winter 2021
Ch.5b − Slide.9

C CO O
PE spectrum helps link
MOs to molecule’s real
structure (vs Lewis):
- 10.7 eV
• 3σ = mostly nonbonding
(a lone pair)
↑
eV - 15.9 eV

• 2x 1π = strongly bonding
(2 π bonds)
- 19.4 eV
• 2σ* = slightly antibonding
(a lone pair)
- 32.4 eV

• 1σ = ? not seen
(must be σ-bond)

See Miessler Fig. 5.13

Fig. adapted from: Shriver & Atkins, Freeman
 CHEM 241

© Drs. XO, PHB, RN, AJH, & CWR

M.O.s for Carbon Monoxide - :C≡O: + Winter 2021
Ch.5b − Slide.10

Fig. adapted from: Shriver & Atkins, Freeman

Miessler This diagram is very similar

Fig. 5.13 C CO O to that used for Li2 to N2,
except that the energies of
the atomic orbitals of
O < C because χO > χC.

- 10.7 eV
CO is isoelectronic with N2
↑ (triple bond + 2 lone pairs).
eV - 15.9 eV Prove it: find bond order.

Why care about MOs?

The HOMO and LUMO
- 19.4 eV are important in the
behaviour of CO, e.g., in
- 32.4 eV
complexes with transition
metals (CO acts as e--pair
donor “σ-base” via its
PE spectrum vibrational structure helps picture MOs: HOMO & e--pair acceptor
(1) 3σ = mostly nonbonding (3) 2σ* = slightly antibonding “π-acid” via its LUMO).
(2) 1π = strongly bonding (4) 1σ = ? (not seen) Details in CHEM341.
 CHEM 241
Other Heteronuclear Diatomics - Question Winter 2021
© Drs. XO, PHB, RN, AJH, & CWR Ch.5b − Slide.11

The diagram for CO is reproduced here,

but it is similar for other isoelectronic
diatomic ions.
How should the left, centre and right
hand energy levels be labelled?

Which labelling is correct?

A. None of them
1) N NO+ O  B. 1) and 3)
2) O NO+ N C. 1) and 4)
3) C CN- N  D. 2) and 3)
4) N CN- C E. 2) and 4)
 CHEM 241

© Drs. XO, PHB, RN, AJH, & CWR

Polyatomics -The General Approach Winter 2021
Ch.5b − Slide.12

There are several methods of setting up the molecular orbital description of

polyatomic molecules. In the lectures, the method used will be as follows:
1) Separate the central atom from the peripheral atoms bonded to it (the ligands).
2) Sketch out the energy levels of the appropriate valence orbitals of the
central atom and of the ligand atoms (those suited to making bonds!).
3) Describe the ligand combinations (group orbitals). The derivation of
these combinations by group theory is beyond the scope of CHEM241 (see
Ch.4 if interested or have taken adv. organic), but the results will be shown.
4) Sketch the energy levels of the ligand combinations (which will differ only
a little from the atomic levels because the ligands are far apart).
5) Make linear combinations of the suitable atomic orbitals on the central atom
with the ligand combinations.
6) Sketch the molecular levels.
7) Distribute the valence e-s according to the aufbau principle & Hund's rule.
8) Work out the bond orders for the equivalent two-centre Lewis-style bonds.
 CHEM 241

© Drs. XO, PHB, RN, AJH, & CWR

A Linear Triatomic Molecule - BeH2 Winter 2021
Ch.5b − Slide.13

Be BeH2 Ha, Hb Ha, Hb

(combos)
2px, 2py, 2pz

2s

1sHa, 1sHb

(The molecular axis will be taken as z)

1) Separate the central atom (Be) from the peripheral atoms bonded to it (the 2 H’s).

2) Sketch out the energy levels of the valence orbitals of the central atom and of
the ligand atoms.
(Hydrogen is more electronegative than Be, so the hydrogen 1s orbitals are at lower
energy than Be’s valence orbitals.)
 CHEM 241

© Drs. XO, PHB, RN, AJH, & CWR

BeH2 Molecular Orbitals (2) Winter 2021
Ch.5b − Slide.14

Be BeH2 Ha, Hb Ha, Hb

(combos)
2px, 2py, 2pz
Group orbitals = sets of matched orbitals
on the peripheral atoms (as if no central
atom, just combinations of outer atoms)
2s
ψ2*
1s(Ha), 1s(Hb)

ψ1
3) Describe the set of symmetry derived ligand orbital combinations (group orbitals)
1 1
ψ1 = (ψ1s ( Ha ) + ψ1s ( Hb) ) and ψ*2 = (ψ1s ( Ha ) − ψ1s ( Hb) )
2 2
+ -
- ψ2*
+ +

+ +
1s(Ha) 1s(Hb) + ψ1

4) Sketch the energy levels of the ligand combinations (group orbitals).

 BeH2 Which central-atom orbitals match up CHEM 241
Winter 2021
© Drs. XO, PHB, RN, AJH, & CWR MOs (3) with the symmetry of the group orbitals? Ch.5b − Slide.15
5) Make linear combinations of the suitable (correct symmetry) atomic orbitals on
the central atom with the ligand combinations.
1 1
σ2 = (ψ 2 + ψ 2 p z ( Be) ) and σ*4 = (ψ 2 − ψ 2 p z ( Be) )
2 2

- σ 4*
+ ψ2p
z (Be)
Ψ 2*
- ψ2p
z (Be)
+ σ2

1 1
σ1 = (ψ1 + ψ 2 s ( Be) ) and σ*3 = (ψ1 − ψ 2 s ( Be) )
2 2
+ ψ2s(Be)
- σ 3*

ψ1

+ σ1
- ψ2s(Be)
 CHEM 241

© Drs. XO, PHB, RN, AJH, & CWR

BeH2 Molecular Orbitals (4) Winter 2021
Ch.5b − Slide.16

6) Sketch the molecular levels.

Be BeH2 Ha, Hb Ha, Hb
(combos)
σ 4*
σ4*

2px, 2py, 2pz

σ3* σ 3*

2πx, 2πy

2s
Ψ 2* 1sHa, 1sHb σ2
ψ1
σ2

σ1
σ1

Remember: the Be 2px and 2py were not used, so

they become non-bonding. They are now MOs, so
are renamed 2πx and 2πy (but they are Be-centered).

7) Distribute the valence electons according to the aufbau principle & Hund's rule.
Here there are four: two from Be (2s2) and one from each H (1s1).
 CHEM 241

© Drs. XO, PHB, RN, AJH, & CWR

BeH2 Molecular Orbitals (5) Winter 2021
Ch.5b − Slide.17

VB-style pictures: MO-style pictures: calculated boundary surfaces of

the molecular orbitals

σ 4*

σ 3*

σ2 2px, 2py

σ1
 CHEM 241

© Drs. XO, PHB, RN, AJH, & CWR

Polyatomics -The General Approach Winter 2021
Ch.5b − Slide.18

There are several methods of setting up the molecular orbital description of

polyatomic molecules. In the lectures, the method used will be as follows:
1) Separate the central atom from the peripheral atoms bonded to it (the ligands).
2) Sketch out the energy levels of the appropriate valence orbitals of the
central atom and of the ligand atoms (those suited to making bonds!).
3) Describe the ligand combinations (group orbitals). The derivation of
these combinations by group theory is beyond the scope of CHEM241 (see
Ch.4 if interested or have taken adv. organic), but the results will be shown.
4) Sketch the energy levels of the ligand combinations (which will differ only
a little from the atomic levels because the ligands are far apart).
5) Make linear combinations of the suitable atomic orbitals on the central atom
with the ligand combinations.
6) Sketch the molecular levels.
7) Distribute the valence e-s according to the aufbau principle & Hund's rule.
8) Work out the bond orders for the equivalent two-centre Lewis-style bonds.
 CHEM 241

© Drs. XO, PHB, RN, AJH, & CWR

BeH2 Molecular Orbitals (6) Winter 2021
Ch.5b − Slide.19

Be BeH2 Ha, Hb Ha, Hb

(combos)
σ4*

σ3*
2px, 2py, 2pz

2px, 2py

2s
ψ2 1sHa, 1sHb

ψ1
σ2

σ1

8) Work out the bond orders for the equivalent two-centre Lewis style bonds.
There are four electrons in bonding orbitals, but both molecular orbitals
extend over the entire BeH2 unit (two 3-centre, 2-electron bonds), so
the equivalent of a single bond can be assigned to each BeH link:
(# bonding electrons - # antibonding electrons) /2 (4/2)
B.O. per BeH link = = = 1
(# of equivalent 2-centre bonds) (2)

Non-classical bonding (not revealed by VB theory): bonding e-s delocalized.

 CHEM 241

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VB vs MO Theory Winter 2021
Ch.5b − Slide.20

Both theories are very much needed to help determine the structure of a molecule

VB theory  based off of valence electrons

MO theory  describes structure more in depth and includes other parameters such
as overlap and energies of the bonding and antibonding e-s

Bad news  MO theory is more involved and difficult

Good news  gives a more complete picture of the structure of a chosen molecule

So what do we do? We cannot ignore one in favor of the other….it would limit our
ability to describe the bonding in molecules
 CHEM 241

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VB vs MO Theory Winter 2021
Ch.5b − Slide.21

VB MO

- Uses overlap of hybrid orbitals to - Make MOs from the combination of

achieve its results atomic orbitals
- Area of overlap is where bonds are - MOs are delocalized over the
formed and localized molecule
- The theory of orbital hybridization can - AOs are most effectively combined if
be used for more complex molecules. they have similar energy and
Hybrid orbitals created from the symmetry (gets complicated fast see
mixing of atomic orbitals Chapter 5c)
- Hybrid orbitals are degenerate and - Unique point: creation of bonding and
only the required number of hybrid antibonding MOs (form by adding the
orbitals are created. Hybrid orbitals wavefunctions of e- constructively or
only represent σ bonding or lp’s destructively)
- Usually start with Lewis structure and - Can allow us to tell the stability of a
use VB to describe if molecule can molecule (via bonding/antibonding
form MOs)
 CHEM 241

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VB vs MO Theory Winter 2021
Ch.5b − Slide.22

VB MO

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