Lecture 24: Applications of Valence Bond Theory The material in this lecture covers the following in Atkins.

14 Molecular structure Valence-bond theory 14.2 Homonuclear Diatomic Molecules 14.3 Polyatomic Molecules Lecture on-line Applications of Valence Bond Theory (PowerPoint) Applications of valence Bond Theory (PDF) Handout for this lecture

Valence Bond Theory

Applications

I. Diatomics H H A 1sH; B

1sH

(1,2) = [A(1)B(2)+ A(2)B(1)] [ (1) (2) (1) (2)]

- bond: invarient to rotation

A B

In general we write (re ,RN ) as the product of electron pair functions i(r2i1, r2i ) as (re , RN ) 1(r1, r2 ) 2 (r3 , r4 ) .. i (r2i 1, r2i ) j (r2 j 1, r ).. 2j n (r2n 1, r2n )

Pair 1 Pair 2

Pair i

Pair j

Pair n

Valence Bond Theory

H Cl

Atomic orbitals on H (Hydrogen)

1sH

Applications (1,2) = [A(1)B(2)+ A(2)B(1)] [ (1) (2) (1) (2)] Hybride orbitals on H (Hydrogen)

1s A

Hybride orbitals on Cl (Chlorine)

sp(B) 1 : [3s + 3pz ] +

Atomic orbitals on Cl (Chlorine)

3s

Cl

Cl 3pCl 3pCl 3py z x

sp(B) : 1 [3s 3p ] z

3pCl 3pCl x y

Valence Bond Theory Electron pairing and formation of bonds

(1,2) = [A(1)B(2)+ A(2)B(1)] [ (1) (2) (1) (2)]

A = 3pCl;B = 3pCl x x for lone-pair
H
Cl

A = 1sH;B = for - bond

sp(Cl) H +

Cl

Electron pairing and formation of lone-pairs

A = sp(Cl);B = sp(Cl) for lone-pair
H
Cl

3pCl x
A = 3pCl;B = 3pCl y y for lone- pair
H
Cl

3pCl y

Valence Bond Theory Applications

Cl Cl

(1,2) = [A(1)B(2)+ A(2)B(1)] [ (1) (2) (1) (2)]

Atomic orbitals on Cl # 1

Hybride orbitals on Cl # 1

3sCl

Cl 3pCl 3pCl 3py z x

sp(Cl) +

sp(Cl) Cl 3pCl y 3px

Atomic orbitals on Cl # 2

Hybride orbitals on Cl # 2

3s

Cl

Cl 3pCl 3pCl 3py z x

sp(Cl) +

sp(Cl) Cl 3pCl y 3px

Valence Bond Theory Applications (1,2) = [A(1)B(2)+ A(2)B(1)] Cl Cl [ (1) (2) (1) (2)]

Electron pairing and formation of bonds A= +

sp(Cl1)

Cl1 A = 3pCl1; B = 3p x x for lone-pair

;B = +
Cl

sp(Cl2)
Cl

bond
Electron pairing and formation of lone-pairs

3pCl x

Cl

Cl

A = 3pCl;B = 3pCl y y for lone- pair

A = sp(Cl1) ;B = sp(Cl1) for lone-pair

Cl
Cl

3pCl y

Cl

Cl

Same for Cl # 2

Valence Bond Theory

Applications

(1, 2 ) = [A(1)B(2) + A(2)B(1 )] [ (1) (2) (1) (2)]

The orbital overlap and spin-pairing between electrons in two collinear p orbitals that result in the formation of a ( bond.

Valence Bond Theory

Applications
(1, 2 ) = [A(1)B(2) + A(2)B(1 )] [ (1) (2) (1) (2)]

I. Diatomics
N N

A= + ;B = + for - bond

sp(1)

sp(2)

1 sp(1) : [2s + 2pz ] + 2

A = sp(1) ; B = sp(1) for lone-pairs

1 sp(1) : [2s 2pz ] + 2
A = 2p1 ;B = 2p1 x x

A = 2p1 ;B = 2p1 y y bonds

Orbitals change sign on reflexation in plane containing 1- 2 bond vector

Valence Bond Theory

Applications
(1, 2 ) = [A(1)B(2) + A(2)B(1 )] [ (1) (2) (1) (2)]

I. Diatomics

The structure of bonds in a nitrogen molecule, which consists of one band and two bands. The electron density has cylindrical symmetry around the internuclear axis.

Valence Bond Theory

Applications

2. Linear molecules
H C C H

A representation of the structure of a triple bond in ethyne; only the bonds are shown explicitly. The overall electron density has cylindrical symmetry around the axis of the molecule.

Valence Bond Theory 3.Trigonal planar

H C H C2H4 C HH
tr3

Applications

H H
C CH2O O

C2H4

x tr1 tr2 y

tr1 tr2 tr3

1 [s px ] 3 1 1 [s px 3 2 1 1 [s px 2 3

CH2O

3 py ] 2 3 py ] 2

Valence Bond Theory 3.Trigonal planar

H C H C2H4 C H H

Applications

(a) An s orbital and two p orbitals can be hybridized to form three equivalent orbitals that point towards the corners of an equilateral triangle. (b) The remaining, unhybridized p orbital is perpendicular to the plane.

C2H4

Valence Bond Theory

4.Tetrahedral
H H C H z H

Applications

sp

hybrides

1 [s p x p y 2 along (x, y, z) t1 1 t2 [s p x p y 2 along (-x, -y, z)

pz ]

pz ]

t2 t1

1 [s p x py 2 along (-x, y, -z) t3

y

pz ]

X t4

t3

1 [s p x py 2 along (x, -y, -z) t4

pz ]

Valence Bond Theory

Applications

4.Tetrahedral sp3

hybrides
H

H C H H

An sp3 hybrid orbital formed from the superposition of s and p orbitals on the same atom. There are four such hybrids: each one points towards the corner of a regular tetrahedron. The overall electron density remains spherically symmetrical.

Valence Bond Theory

Applications
H H C H H

4.Tetrahedral

sp3

hybrides

A more detailed representation of the formation of an sp3 hybrid by interference between wavefunctions centred on the same atomic nucleus. (To simplify the representation, we have ignored the radial node of the 2s orbital.)

Valence Bond Theory

Applications

4.Tetrahedral
sp3 hybrides
z

(1, 2 ) = [A(1)B(2) + A(2)B(1 )] [ (1) (2) (1) (2)]

z
z

t2 t1 y X t4

t2 t1 y X
t3
X t4

t2 t1 y

t3

t3

t4

H H C H H

N H

O H

Valence Bond Theory

4.Tetrahedral sp3

Applications hybrides (1, 2 ) = [A(1)B(2) + A(2)B(1 )] [ (1) (2) (1) (2)]

z

t2 t1 y X t4

O H

t3

use of sp 3 hybrides
A first approximation to the valence-bond description of bonding in an H2O molecule. Each bond arises from the overlap of an H1s orbital with one of the O2p orbitals. This model suggests that the bond angle should be 90, which is significantly different from the experimental value.

Use of p - orbitals

Valence Bond Theory 5.Bipyramidal

F F S F F F P F F F x F

Applications
hybrides
tr3
d4 z

d2 sp2

tr1 tr2
d5

tr1 tr2 tr3

1 [s px ] 3 1 1 [s px 3 2 1 1 [s px 3 2

3 py ] 2 3 py ] 2

d4 d5

1 [pz 2 1 [pz 2

z2

d 2]
z

Valence Bond Theory 5.Bipyramidal d2 sp2 hybrides

Applications

(1, 2 ) = [A(1)B(2) + A(2)B(1 )] [ (1) (2) (1) (2)]

F F P F F F

F F S F F

Valence Bond Theory

Applications

6. Octahedral
d2 sp 3
z

hybrides
oc1

(1, 2 ) = [A(1)B(2) + A(2)B(1 )] [ (1) (2) (1) (2)]

1 [s 6 2dz 2 3pz ]

4 5

1 3 2 6 x

oc2 oc3 oc4

1 [s 6

1 d 2 2 z

3 d 2 2 x

y2

3p x ]

oc5
oc6

1 1 3 [s d2 d 2 2 3p y ] z x y 6 2 2 1 1 3 [s d2 d 2 2 3px ] z x y 6 2 2 1 1 3 [s d2 d 2 2 3p y ] z x y 6 2 2
2dz 2 3pz ]

1 [s 6

Valence Bond Theory

Applications

6. Octahedral
d2 sp 3 hybrides
z

(1, 2 ) = [A(1)B(2) + A(2)B(1 )] [ (1) (2) (1) (2)]

F
y

F F

F F
x

S F

What you should learn from this lecture

1. You are not required to know the mathematical form of the s and p atomic orbitals as well as the sp,sp2, sp3 , sp 2d2 , sp 3d2 hybrides. However you should be able to draw their shapes

2. You should be able to convert Lewis structures based on bonds and lone pairs into valence bond pair functions (1, 2 ) = [A(1)B(2) + A(2)B(1 [ (1) (2) (1) (2)] )] where A and B are atomic orbitals (or hybrides) on different centers for bonds ,and orbitals on the same center for lone-pairs