13 PDF
13 PDF
Molecular Orbital
1
Chem 104A, UC, Berkeley
Resonance
The best structure has the fewest formal charges and has
the negative charge on the highest electronegativity atom.
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Chem 104A, UC, Berkeley
Mulliken
Unoccupied orbital
Spectroscopic properties
(ionization, excited states)
bonds: have
bonds: a node on the
symmetric about inter-nuclear axis
the internuclear and the sign of
axis the lobes
changes across
the axis.
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Chem 104A, UC, Berkeley
Valence Bond Theory
Valence bond theory treatment of bonding in H2 and F2
F
2s 2p
HA 1s1 HB 1s1
F
A B 2s 2p
z axis
2pz 2pz
z axis O
2s 2p
2pz 2pz
This gives a 2p-2p bond O
between the two O atoms. 2s 2p
z axis
O O
Lewis structure
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Chem 104A, UC, Berkeley
A B
0.74 A
Our Goal
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Chem 104A, UC, Berkeley
1 1 3 / 2 r / a0
Energy 1s ( ) e
a0
a
1s A (1) 1sB (2)
0
-2
f Experimental curve
-4 eV
a
b
0
f Experimental curve
-4 eV
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Chem 104A, UC, Berkeley
Variation Principle:
( x) H ( x)dx
*
H
* ( x) ( x)
Variation Principle:
(x)
Can always minimize E ( x ) ( x)
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Chem 104A, UC, Berkeley
1 1 3 / 2 r / a0
1s () e
a0
+ +
1 Z 3 / 2 Zr / a0
1s 100 () e
a0
a
b
0 c
1s A (1) 1sB (2) 1s A (2) 1sB (1)
-2 Zeff=1.17
f Experimental curve
-4 eV
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Chem 104A, UC, Berkeley
Promoting electron
Orbital Hybridization
- + +
A
1s A
2pzA A N (1s A 2 p zA )
B N (1sB 2 p zB )
+ + - B
1s B
2pzB
1
1 2
s contribution
2
p contribution
1 2
- + + A N (1s A 2 p zA )
A
1sa 2pza
B
+ + -
B N (1s B 2 p zB )
1sb 2pzb
=0.1
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Chem 104A, UC, Berkeley
Energy
A N (1s A 2 p zA )
g
B N (1sB 2 p zB )
a
b
0 c
a
b
0 c
f Experimental curve
=6%
-4 eV
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Chem 104A, UC, Berkeley
Energy Valence bond theory is all about promoting e
and hybridizing orbitals into the shape required by
experiments.! g
a
b
0 c
-2 d
e
f
-4 eV
Covalent Bond
- F N (2 p zF 2s F )
+ +
+ + H1s
2sF 2pzF
lp N (2 p zF 2sF )
- + +
+ H
+
2sF 2pzF
=0.5 Lone pair
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Chem 104A, UC, Berkeley
promotion
1s 2 2s 2 2 p x2 2 p y2 2 p1z 1s 2 2 s1 2 p x2 2 p y2 2 p z2
E 500kcal / mol
1 eV=96.4 kJ/mol=23.1 kCal/mol
Benefit of hybridization
1. Increase in e density between nuclei, enhanced bonding
2. Decrease in e-e repulsion by formation of a lone-pair
orbital, LP Orbital more directed away from BP than the
Original s LP
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Chem 104A, UC, Berkeley
[1sHa (1)2 p yo (2) 1sHa (2)2 p yo (1)] [1sHb (3)2 p zo (4) 1sHb (4)2 p zo (3)]
Chem 104A,
Valence bond theory is all about promoting UC, Berkeley
electron
and hybridizing orbitals into the shape required by
experiments!
-
y py s
+ O -
104.5
+ pz
H H
dv 0
b
a b
a
a dv 1
2
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Chem 104A, UC, Berkeley
-
y py s
+ O -
+ pz
H H
a b
z
a N [cos 2 p zo sin 2 p yo 2so ]
2 2
b N [cos 2 p zo sin 2 p yo 2so ]
2 2
Normal means that the integral of the product of an orbital with itself is equal
to 1, i.e.:
1
n n
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Chem 104A, UC, Berkeley
a N [cos 2 p zo sin 2 p yo 2so ]
2 2
b N [cos 2 p zo sin 2 p yo 2so ]
2 2
104.5 dv 0
a b
Orthogonality
0.5
dv 1
2
Normalization
a N 1 / 1.25
[1sHa (1)2 p yo (2) 1sHa (2)2 p yo (1)] [1sHb (3)2 p zo (4) 1sHb (4)2 p zo (3)]
New Wavefunction:
[1sHa (1) a (2) 1sHa (2) a (1)] [1sHb (3)b (4) 1sHb (4)b (3)]
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a 0.55 Chem
2 p zo 104A,
0.71 2Berkeley
UC, p yo 0.452 2so
Orbital contribution 0.55 2 p 0.712 2 p 0.452 2s
b zo yo o
a b
30% 30% 60%
2 p zo 0.55 30%
2
-
y py s
+ O - lp 0.63 2 p zo 0.77 2so
+ pz
H H
a b
z
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Chem 104A, UC, Berkeley
p s
1
lp1 (2 p x lp ) character character
2
lp1
1
(2 p x lp ) Bonding 80% 20%
2 orbital
lp 70% 30%
orbital
2s 2p
N
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Chem 104A, UC, Berkeley
H N H 107.3
p s
character character
Bonding 77% 23%
orbital
lp 69% 31%
orbital
1s 2 2 s 2 2 p 0 Promotion 1s 2 2s1 2 p1
1
Chem 104A, UC, Berkeley
1
a (2 s 2 p x )
2
1
b (2s 2 px )
2
p s
character character
Bonding 50% 50%
orbital
2
Chem 104A, UC, Berkeley
A 2s orbital superimposed 1 1
on a 2px orbital 1 s p The two resultant sp
2 2
hybrid orbitals that are
1 1 directed along the x-axis
2 s p (in this case)
2 2
The 1/2 are normalization coefficients.
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Chem 104A,
Example of the orthogonality of 1UC,
andBerkeley
2
1 1 1 1
1 s p 2 s p
2 2 2 2
1 1 1 1
1 2
2
s p
2 2
s p
2
2 2 2 2
1 1 1 1
1 2 s s s p s p p p
1 1 1 1
2 1 2 0 2 0 2 1
1 2
1 1
2 2 0
1 2
2H
1s 1s
H Be H
The overlap of the hybrid orbitals on Be with the 1s orbitals on the H
atoms gives two Be-H (sp)-1s bonds oriented 180° from each other.
This agrees with the VSEPR theory prediction.
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Chem 104A, UC, Berkeley
p s
character character
Bonding 67% 33%
orbital
Valence bond theory treatment of a trigonal planar molecule: the bonding in BH3
2s 2p
B
B*
sp2 2p
B* (sp2)
1 1 1
1 s p p
y This gives three sp2 orbitals 3 6 x 2 y
that are oriented 120° 1 1 1
apart in the xy plane – be 2 s px p
3 6 2 y
x careful: the choice of axes
1 2
in this example determines 3 s p
3 6 x
the set of coefficients.
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Chem 104A, UC, Berkeley
1 2 3: +x, 0y
3 s p 1/3 + 4/6 = 1
3 6 x So this hybrid is normal y
Valence bond theory treatment of a trigonal planar molecule: the bonding in BH3
sp2 2p
B*
3H
1s 1s 1s
H
H B
H
The overlap of the sp2 hybrid orbitals on B with the 1s orbitals on the H
atoms gives three B-H (sp2)-1s bonds oriented 120° from each other.
This agrees with the VSEPR theory prediction.
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Chem 104A, UC, Berkeley
p s
character character
Bonding 75% 25%
orbital
2s 2p
C
C*
sp3
C* (sp3)
1 1 1 1
1 s p p p
This gives four sp3 orbitals 4 4 x 4 y 4 z
that are oriented in a 1 1 1 1
H 2 s p p p
tetrahedral fashion. 4 4 x 4 y 4 z
H C H 3
1
s
1
p
1
p
1
p
4 4 x 4 y 4 z
H 1 1 1 1
4 s p p p
4 4 x 4 y 4 z
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Chem 104A, UC, Berkeley
2s 2p
C
C*
sp3
C* (sp3)
4H H
1s 1s 1s 1s
C H
H
H
The overlap of the sp3 hybrid orbitals on C with the 1s orbitals on the H
atoms gives four C-H (sp3)-1s bonds oriented 109.47° from each
other. This provides the tetrahedral geometry predicted by VSEPR
theory.
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Chem 104A, UC, Berkeley
1
Chem 104A, UC, Berkeley
Trigonal bipyramidal
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Chem 104A, UC, Berkeley
Valence bond theory treatment of a trigonal bipyramidal molecule:
the bonding in PF5
3s 3p PF5 has a VSEPR theory AX5
P geometry so we need hybrid
3d orbitals suitable for bonds to
P* 5 atoms. ns and np
combinations can only
P* (sp3d) 3d provide four, so we need to
use nd orbitals (if they are
available).
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Chem 104A, UC, Berkeley
Valence bond theory treatment of a trigonal bipyramidal molecule:
the bonding in PF5
P* (sp3d) 3d
F
2s 2p
F F
2s 2p 2s 2p
F
2s 2p
F
2s 2p
The overlap of the sp3d
hybrid orbitals on P with the 2p orbitals on the F
atoms gives five P-F (sp3d)-2p bonds in two sets: the two axial bonds
along the z-axis (180° from each other) and three equatorial bonds in
the xy plane (120° from each other and 90° from each axial bond).
This means that the 5 bonds are not equivalent!
octahedral
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Chem 104A, UC, Berkeley
Valence bond theory treatment of an octahedral molecule:
the bonding in SF6
3s 3p
S
3d
S*
S* (sp3d2) 3d
F F F F F F
The overlap of the sp3d2 hybrid orbitals on S with the 2p orbitals on the F
atoms gives six S-F (sp3d2)-2p bonds 90° from each other that are
equivalent. You can figure out the normalization coefficients.
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Chem 104A, UC, Berkeley
Valence bond theory treatment of bonding: a hypervalent molecule, ClF3
3s 3p F
Cl
3d
F Cl
Cl* F
There are five “objects” around
Cl* (sp3d) 3d
Cl so the geometry is trigonal
bipyramidal and the shape is
F F F given by AX3E2 (T-shaped).
The overlap of the sp3d hybrid orbitals on Cl with the 2p orbitals on the F
atoms gives three P-F (sp3d)-2p bonds in two sets: the two axial bonds
along the z-axis (less than 180° from each other because of the
repulsion from the lone pairs) and the one equatorial bond halfway
between the other Cl bonds. Again, the bond lengths will not be the
same because there is more d contribution to the axial hybrid orbitals.
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Chem 104A, UC, Berkeley