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Molecular Orbital Theory: Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology
Molecular Orbital Theory: Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology
Molecular Orbital Theory: Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology
Edward A. Mottel
Department of Chemistry
Rose-Hulman Institute of Technology
Bonding Theories
Ionic Model
Skeleton Diagrams
Lewis Dot Diagrams
• Formal Charge, Resonance
Molecular Orbital Theory
• Extends atomic orbitals concepts to
molecules
04/12/23
Bonding in Diatomic Molecules
Diatomic: molecule contains two atoms
••
•
•
••
A+ •• B •• •• C •• D ••
••
•
•
••
Ionic bonding Covalent bonding
large difference in small difference in
electronegativity electronegativity
04/12/23
Heterodiatomic Molecules
HF, BN and CO are heterodiatomic molecules.
H-F
positive end negative end
What is an orbital?
a bond forms
1s atomic 1s atomic
orbital orbital
sb molecular
orbital
sigma s bonding molecular orbital
04/12/23
Molecular Orbitals
nuclei
(sb)2 molecular
orbital
04/12/23
Molecular Orbitals (mo)
Obey many of the same rules as atomic
orbitals (ao).
• two electrons per molecular orbital.
• specific regions of space.
• one molecular orbital formed for each
atomic orbital used.
04/12/23
Wave Functions
The amplitude (height) of each wavefunction
can either be positive or negative.
04/12/23
Wavefunctions
Bonding & Antibonding Orbitals
b
*
04/12/23
Bonding & Antibonding Orbitals
sb When a bonding
molecular orbital forms,
an antibonding
molecular orbital
H H also forms.
s*
04/12/23
Atomic and Molecular Orbitals
Atomic orbitals include
z
y
x
1s 2py 3dz2
04/12/23
Atomic and Molecular Orbitals
Molecular orbitals include
z
y
x
s b
x* z*
04/12/23
Atomic and Molecular Orbitals
04/12/23
Atomic and Molecular Orbitals
carbon: 1s2 2s2 2p2
energy
04/12/23
Dihydrogen, H2
H H
s*
energy
sb
H H
The branch lines indicate which Two 1s1 hydrogen orbitals
atomic orbitals are involved in overlap to form a sb
generating the molecular orbitals.
bonding molecular orbital
1s1 hydrogen orbital
04/12/23 of two hydrogen atoms
Dihydrogen, H2
What advantage can
an orbital gain in forming
s* a molecular orbital from
energy
an atomic orbital?
H H
s
b
ao mo ao Dihydrogen is diamagnetic
(s )
b 2
and contains one bond
electronic configuration (one pair of bonding electrons).
of the hydrogen molecule.
Why is dihydrogen
diamagnetic?
04/12/23
Dihelium, He2
Two electrons occupy
s* the highest
Eachmolecular
helium atomorbital
energy
forming
has a s*
the electronic
configuration 1s2
Two (each contributes
electrons occupy
sb
the 2lowest
electrons to the helium
molecular orbital
molecular orbitals)
atomic orbital atomic orbital forming a s
b
04/12/23
Dihelium, He2
as a stable molecule?
04/12/23
Dihelium(I) Ion, He2+
He He
s*
energy
He He+
sb
He He+
sb
Shaded means
2 electrons
Lined
means 1
04/12/23
Dihelium(I) Ion, He2+
s*
energy
He He+
sb
Draw an outline
Fill-in theof the molecular
molecular orbitals.
orbitals,
shaded for 2 electrons, lined for 1.
04/12/23
Dihelium(I) Ion, He2+
04/12/23
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.
04/12/23
Orbitals Are Wave Functions
04/12/23
Pi Bond Formation
The molecular orbital
y does not lie directly on y
the internuclear axis.
z z
04/12/23
Antibond Formation
What is the symbol of a antibond?
How is a antibond formed?
What does a antibond look like?
Pi Antibond Formation
y y
z z
04/12/23
Pi Bonds
y* yb
04/12/23
Pi Bonding Involving Px Orbitals
x x
xb
Resulting Bonding
px- px Orbital Overlap Molecular Orbital
04/12/23
Pi Bonding Involving Px Orbitals
x x
x*
04/12/23
Pi Bonding Involving p Orbitals
2p
px-px overlap gives and x*
x
b
y
py-py overlap gives y and y*
b
energy
overlap
direction 2s
energy
1s
04/12/23
Molecular Orbital Diagrams
Involving s and p Orbitals
Nonbonding
Antibonding
Bonding
Pi bonds
Sigma molecular
molecular
andand
bonds
antibonds
orbitals 2s
antibonds
Homonuclear
energy
2p Examples:
Li2, B2, C2, N2
Heteronuclear
2s Examples:
NO, BO, BO+,
CO, CO+,
1s CN, CN–
04/12/23
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.
04/12/23
Orbital Sequence
(sn) (sb) (s*) (x,yb) (zb) (x,y*) (z*)
z*
x,y*
energy
2p
zb
x,yb
s*
2s sb
1s sn
04/12/23
Dinitrogen
Diberyllium
Dicarbon
Diboron (14
Dilithium(10
(12
(6 total
(8total
total
total ––e––)
eee )) )
Complete
Bondthe
Order
mo diagram
and Magnetic
for Li2Properties?
, Be2, B2, C2 or N2
z*
x,y*
2p
zb
x,yb
energy
s *
2s
First, sb Then,
fill in the fill in the
valence
1s sn mo diagram
electrons.
04/12/23
Compare the bond order, bond length and
magnetic properties of O2, O2+ , O2– and O22–
energy z*
x,y*
2p
x,yb
zb
2s s*
O 2
–+
2–
sb
1.123
1.207
1.26 Å
1.49 Å
Å
properties?1s sn
04/12/23
Dioxygen
•• ••
•• ••
O •• •• O
•• ••
•• ••
O •• •• O
04/12/23
Oxygen-Oxygen Bonds
•• ••
•• ••
••
••
O O H O O H
••
••
Which oxygen-oxygen bond is easier to break?
Difluorine
Dineon (20(18total
totalee))
––
energy z*
x,y*
2p
x,yb
zb
2s s*
sb
1s sn
04/12/23
Homodiatomic Molecules
bond
bond
length magnetic
Electronic Configuration order properties
(Å)
H2 (sb)2 1 0.74 diamagnetic
04/12/23
Homodiatomic Molecules
Electronic Configuration
04/12/23
Homodiatomic Molecules
bond bond magnetic
order length (Å) properties
C2 2 1.31 diamagnetic
N2 3 1.10 diamagnetic
O2 2 1.207 paramagnetic
F2 1 1.42 diamagnetic
Ne2 0
04/12/23
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