Molecular Orbital Theory

Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology

A Little Review
What is an orbital? Give an example of an atomic orbital? What is the name of the mathematical function that determines the shape of an orbital? What is the maximum number of electrons that can be in one orbital?

Molecular Orbitals
When two atoms come close to each other, what happens to the orbitals of each atom?

a bond forms
1s atomic orbital 1s atomic orbital ssb molecular orbital
sigma s bonding molecular orbital
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Molecular Orbitals
Orbital wave functions can add & subtract to give new wave functions and corresponding molecular orbitals (mo). Atoms bond together when the wave functions constructively overlap.
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SIGMA BOND (s)

A bond between two atoms in which the electron density of the molecular orbital is between the two nuclei is called a sigma bond. nuclei (ssb)2 molecular orbital

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Molecular Orbital Theory

Atomic orbitals can mix together to give a new set of molecular orbitals.
One molecular orbital is formed for each atomic orbital used Similarities of atomic & molecular orbitals 2 electrons max/orbital occupy specific regions of space
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Orbitals Are Wave Functions

Wave functions contain mathematical terms that can have positive and negative values. An s orbital value can either be less than zero or greater than zero. The two lobes of a p orbital are separated by a node and have opposite signs.

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Orbitals Are Wave Functions

Different colors represent opposite mathematical signs.

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Sigma Bond Formation

pz- pz Orbital Overlap

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Sigma Bonds
(szb)

pz- pz Orbital Overlap

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Resulting Molecular Orbital

Sigma Antibond Formation

pz- pz Orbital Overlap

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Sigma Antibond Formation

z
(sz*) pz- pz Orbital Overlap
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Resulting Antibonding Molecular Orbital

s indicates the most probable electron position is on the internuclear axis

Sigma Bonds
(szb)
b

indicates a bonding molecular orbital

(sz*) z indicates the molecular orbital involves two pz atomic orbitals

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* indicates an antibonding molecular orbital

Electrons in this orbital will weaken the bonds between these atoms.

Sigma Bonds
(ssb)

z
(ss*)
s indicates the molecular orbital involves at least one s atomic orbital.
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Pi Bond Formation
y
A pi bond (p) occurs when two lobes of each atomic orbital overlap.

py- py Orbital Overlap

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Pi Bond Formation
y
The molecular orbital does not lie directly on the internuclear axis.

py- py Orbital Overlap

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Resulting Bonding Molecular Orbital

p Antibond Formation
What is the symbol of a p antibond?

How is a p antibond formed?

What does a p antibond look like?

Pi Antibond Formation
y y

z
py- py Antibond Orbital Overlap
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z
Resulting Antibonding Molecular Orbital

Pi Bonds

py* py* bonding orbital has four lobes and holds a maximum of two electrons.

pyb pyb bonding orbital has two lobes and holds a maximum of two electrons.

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Pi Bonding Involving Px Orbitals

pxb

px- px Orbital Overlap

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Resulting Bonding Molecular Orbital

Pi Bonding Involving Px Orbitals

x
px- px Antibonding Orbital Overlap
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px*

Resulting Antibonding Molecular Orbital

Pi Bonding Involving p Orbitals

px-px overlap gives px
b and

px*

2p

py-py overlap gives

pyb and

py*

From the mo diagram, how can you determine that pxb and pyb are equally stable? Why are pxb and pyb equally stable?
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Molecular Orbital Diagrams

Involving s and p Orbitals
The molecular orbitals formed depend on the atomic orbitals

2p
energy

overlap direction energy

2s

1s

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Molecular Orbital Diagrams

Involving s and p Orbitals
Identify the orbitals that represent the following Pi bonds Nonbonding molecular Antibonding and Bonding molecular Sigma bonds and antibonds orbitals antibonds Weak pz-s mo interaction Homonuclear examples: O2, F2
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2p

2s

1s

Diatomic Molecular Orbital Diagram

Strong pz-s interaction energy 2p
Homonuclear Examples:

Li2, B2, C2, N2

2s
1s
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Heteronuclear Examples:
NO, BO, BO+, CO, CO+, CN, CN

Homonuclear Diatomic Molecules

Determine

is the sequence of molecular orbitals based on the strong pz-s interaction diagram. Determine the bond order and magnetic properties for homodiatomic molecules of the first nine elements. Show the bond lengths are consistent with these diagrams.

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Orbital Sequence (ssn) (ssb) (ss*) (px,yb) (szb) (px,y*) (sz*) energy

2p

sz* px,y*
szb px,yb s s* ssb ssn

2s 1s
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Dinitrogen(12totalee)) Diberyllium(14totalee)) Dicarbon(10total Dilithium (6 total Diboron (8

Complete the mo diagram for Li2,Properties?2 or N2 Bond Order and Magnetic Be2, B2, C

2p energy

sz* px,y*

First, fill in the valence electrons.

2s 1s

szb px,yb ss* ssb

Then, fill in the ssn mo diagram

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1.123 1.207 1.49 1.26 properties?1s

Compare the bond order, bond length and magnetic properties of O2, O2+ , O2 and O22 sz* px,y* 2p px,yb szb ss* 2 + 2s O2 s sb energy

ssn

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Dioxygen
O O

What are the advantages and disadvantages of this description of dioxygen?

Compare the physical properties predicted for Dioxygen by the Lewis Dot Diagram and MO Theory

O O

Bond Order
Lewis Dot Structure Molecular Orbital Theory

Magnetic Properties ? (diamagnetic) paramagnetic 2 unpaired electrons

Liquid dioxygen will cling to the pole of a magnet.

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Compare the physical properties for the Dioxygenyl(I) Ion, Dioxygen, Superoxide Ion and Peroxide Ion Bond Length Bond Order 2.5 2 Magnetic Properties paramagnetic (1) paramagnetic (2)

O 2+
O2

1.123 1.207

O2
O22

1.26
1.49

1.5
1

paramagnetic (1)
diamagnetic

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Oxygen-Oxygen Bonds

Which oxygen-oxygen bond is easier to break?

O O

H O O H

Difluorine (18 total e)) Dineon (20 total e

Bond Order and Magnetic Properties?

energy

2p

sz* px,y*

2s 1s

px,yb szb ss* s sb ssn

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Homodiatomic Molecules
Electronic Configuration
H2 (ssb)2 He2 (ssb)2 (ss*)2 Li2 (s1sn)4 (ssb)2 Be2 (s1sn)4 (ssb)2 (ss*)2 bond bond length magnetic order properties () 1 0 1 0 1 2.67 diamagnetic 0.74 diamagnetic

B2 (s1sn)4 (ssb)2 (ss*)2 (pxb)1 (pyb)1

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1.59 paramagnetic

Homodiatomic Molecules
bond order C2 N2 O2 F2 Ne2
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bond length () 1.31 1.10 1.207 1.42

magnetic properties
diamagnetic diamagnetic paramagnetic diamagnetic

3
2 1 0

Skeleton Diagram Failures

Carbon Monoxide
C O

or

C O

How would the hybridization of the atoms in carbon monoxide be described?

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energy

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CO

Carbon Monoxide
Sigma orbital overlaps of CO.

+
+ +

+
-

+
+ -

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+ + - + +

+ +

+
-

- ++ -

- + - +

Is the HOMO of carbon monoxide bonding, nonbonding or antibonding? CO 1.1282

CO+

1.1151

Where on carbon monoxide is the HOMO located?

energy

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CO

Species containing three or more atoms

Beryllium Hydride
Draw the orbital overlaps of BeH2.

+ +

+ -

Rank the orbitals in terms of energy.

(draw the nodes in each diagram)

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Draw a molecular orbital diagram of BeH2.

orbitals are conserved

two bonds are formed

all e- are paired energy

Sigma (s) bonds form

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Be

BeH2

2H

Draw the molecular orbital diagram for the nitrate ion. What is the hybridization of nitrogen? How many atomic orbitals are there? How many p-p orbitals are there? How are the energies of the p-p orbitals going to split? How many nonbonding orbitals are expected?
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Nitrate Ion
O

N+ O

The double bond is delocalized over the three nitrogen-oxygen bonds. Bond order = 1.33

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N+ O

O N+ O

Nitrate Ion
What is the hybridization of nitrogen?
-

O N O

1.22

The nitrogen-oxygen bond length is intermediate between N-O and N=O.

typical N-O bond length: 1.40

typical N=O bond length: 1.21

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How do the orbitals of the atoms in nitrate overlap?

Nitrate Ion
O

N+ O

The nitrogen atom in nitrate ion is sp2 hybridized and overlaps a pz orbital on each oxygen.

Top down view (xz plane)

three N - O sigma bonds

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Nitrate Ion
O

N+ O
How does the double bond form?

If you dont believe in hybridization.

Top down view (xz plane)

three N - O sigma bonds

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Nitrate Ion
O

N+ O

pi overlap involves the nitrogen py orbital with all three oxygen py orbitals to form one pi bond the oxygen orbitals with single electrons change from one oxygen atom to another

Edge on view

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Nitrate Ion
this hybridization requires that the nitrate ion is planar

one N - O pi bond delocalized over three oxygen atoms

Edge on view

What would the py-orbitals look like if all four atoms in this ion were not planar?

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Nitrate Ion
if nitrate ion wasnt planar

one N - O pi bond delocalized over three oxygen atoms

Edge on view

What would the py-orbitals look like if all four atoms in this ion were not planar?

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energy

NO3

3O

Sigma Bonding Patterns Nitrogen s, px and py orbitals overlap with oxygen.

energy

NO3

3O

How are the energies of the p-p orbitals going to split?

energy

NO3

3O

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energy

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CO

energy

N O O O