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Lecture 31: Polyatomic Molecules A course evaluation is scheduled for the last 20 minutes of the lecture on Monday March

27 The material in this lecture covers the following in Atkins. 14 Molecular orbitals for polyatomic systems 14.8 Walsh diagrams (a) The Walsh diagram for H2X Lecture on-line Polyatomic Molecules (PowerPoint) Polyatomic Molecules (PDF) Handouts for this lecture

Polyatomic Molecules We shall in the following We shall be using linear develop a simplified model for AH2 and AH3 molecules variation theory to calculate energies based on molecular orbital k=n theory Ck Hik WSik = 0 H A k=1

H A key point will be to understand how the optimal bond angle changes with the number of valence electrons Se H Be H
=180 H H =90

i = 1,n k = 1,n

..express molecular orbitals as a linear combination of atomic orbitals (LCAO)


k=n i= k k Ci p k=1

k = 1,n ; i = 1,n

Polyatomic Molecules The atomic orbitals are : 2sA 1sA

AH2

H1

H2 H1

H2

2pb2 H1 H2 H1

2pa1 H2

The 1s A and 2s A are too low in energy to participate in the bonding with 1s H (core orbitals). They will go unchanged from A over into AH2 each holding 2 electrons

2pb1
1

H2

This is a simplification (approximation) in the case of 2sA

1sH1

1sH2

Polyatomic Molecules The atomic orbitals are :

AH2

The molecular orbitals will be linear combinations of atomic orbitals.


Only atomic orbitals on different centers that overlap will mix To make use of this we make two new combinations of the hydrogen 1s orbitals A
A 1sb2

2pb2 H1 H2 H1

2pa1 H2

2pb1
1

H2

1sH1

1sH2

1sa1

Polyatomic Molecules The atomic orbitals are :

Inspection indicates that AH2 2p will overlap (interact) a1 with 1sa1

2pb2 H1 H2 2pa1

2pa1

2pb1H
1

H2

1sH(a1)
2pb2 with 1sb2 2pb2 A

H2

A
1sb2

1sa1

1sb2 2pb1 will not interact

Heteronuclear diatomic molecules Linear variation theory


- = C A A + CB B

This is an out - of -phase anti - bonding orbital withthe largest contribution from B of highest energy

A
E+
+ + + = C A A + CB B

This is an in - phase bonding orbital with the largest contribution from A of lowest energy

Heteronuclear diatomic molecules

Linear variation theory

| A B | 1. A B or << 1 ||
1 1 - = A + B 2 2

The solutions

E = B 1 S
A

oSAB

A + E+ = 1+ S
B A

+ =

1 1 A + B 2 2

Polyatomic Molecules

AH2

2pa1 H1 H2

1a1 =

1 1 2pa1 + 1sa1 2 2

1sa1

1 1 2a1 = 2pa1 + 1sa1 2 2


The orbital energies are :

The interaction between 2p a1 and 1sa1 will give rise to


..bonding orbital 1a 1 ..anti - bonding orbital 2a1

1a = + o cos( / 2)
1

2a = o cos( / 2)
1

The interaction large for small . It is zero for = 180

1a1

2a1

Polyatomic Molecules

AH2

2pb2 H1 H2

1b2 =

1 1 2pb2 + 1sb2 2 2

1 1 2b2 = 2pb2 + 1sb2 2 2


1sb2 The orbital energies are :
1b = + o sin( / 2)
2

The interaction between 2p b2 and 1sb2 will give rise to

..bonding orbital 1b 2

..anti - bonding orbital 2b2

2b = o sin( / 2)
2

The interaction small for small . It is max. for = 180

1b2

2b2

Polyatomic Molecules Correlation diagram AH2


A 2 b2

AH2

BeH2 and

BH+ 2

Configuration (1b2 )2
2a1 A 2b2

= 180
1b 1

1b 1 H1 H2

H2 H1 1a = + o cos( / 2) 1

BH2 , AlH2

(1b2 )2 (1a1)1

2a1

exp
1a1 1a1 A 1b 2

theor 127 127

BH2 AlH2

131 120

A 1b2

1b = + o sin( / 2)
2

180

90

Polyatomic Molecules Correlation diagram AH2


A 2 b2

AH2
SiH2 , BH2

(1b2 )2 (1a1)2
Theor

exp
2a1 A 2b2

SiH2
1b 1 H2

92 102

90 90

1b 1 H1 H2 H1
1

BH2

2a1

1a = + o cos( / 2)

Configuration (1b2 )2 (1a1)2 1b1 theor = 90

1a1

1a1 A 1b 2

NH2 PH2 AsH2 91 exp 103 92


H2O+ CH2 H2S + 99 93 exp 111

A 1b2

1b = + o sin( / 2)
2

180

90

Polyatomic Molecules AH 2 Correlation diagram AH 2


A 2 b2

Configuration (1b2 )2 (1a1)2 1b1 theor = 90

OH2 SH2 SeH2 91 exp 105 92


2a1 A 2b2

1b 1 H1 H2

1b 1 H2 H1 1a = + o cos( / 2) 1

H2F+ NH2 104 exp 118

2a1

Excited states AH2 Config exp theo NH2 (1b2 )2 (1a1)11b12 144 127

1a1

1a1 A 1b 2

PH2 (1b2 )2 (1a1)11b12 123 127 CH2 (1b2 )2 (1a1)11b11 136 127 SiH2 (1b2 )2 (1a1)11b11 123 127

A 1b2

1b = + o sin( / 2)
2

180

90

Polyatomic Molecules
A 2 b2

AH2

2a1 A 2b2

1b 1 H1 H2 H1

1b 1 H2

2a1

1a1

1a1 A 1b 2

A 1b2

180

90

Polyatomic Molecules

AH3

=120 trigonal planar


=10990 trigonal pyramidal

Polyatomic Molecules
The atomic orbitals are :

AH3

Interactions are possible between (2pa , 1sa ); (2pex , 1sex ); (2pey , 1sey )

2pa

2pex

2pey

1sa

1sex

1sey

Polyatomic Molecules

AH3

BH3; AlH3 : (1e)4


2ex

theo = 120 ; exp = 120


2ey 2ex

2ey

2a

2a

(1e)4 1a 1 AH3 exp CH3 120 SiH3 110 PH3+ 113


(1e)4 1a 2 AH3 exp NH3 108 PH3 93 AsH3 92 SbH3 91

theo 109 109 109


theo 90 90 90 90

1a

1a

1ex 1ey

1ex

1ey

120

90

Polyatomic Molecules

The fragment approach

Organic molecules are made up of sp, sp2 and sp3 carbon centers
sp3 hybrides

C H

C C C H

sp2 hybrides
sp hybrides

Polyatomic Molecules

The fragment approach

Alternatively, organic molecules are made up of CR (sp),CR2 ( sp2 ) and CR3 (sp3 ) fragments

C H

C C C H
1x 1y 2

bonds

bond

1 H C

Polyatomic Molecules

The fragment approach

Alternatively, organic molecules are made up of CR (sp),CR2 ( sp2 ) and CR3 (sp3 ) fragments

C H

C C C
1b1

bonds

bond

1a1

b2

Polyatomic Molecules

The fragment approach

Alternatively, organic molecules are made up of CR (sp),CR2 ( sp2 ) and CR3 (sp3 ) fragments

C H

C C C H
1a1

bond

1ex

1ey

What you must learn from this lecture


1. For EHn (n = 2, 3) you must be able to construct the molecular orbitals as linear combinations of the p - orbitals on the main - group element E and linear combinations of the 1s orbitals on hydrogen
2. Be able to account for the variation in the orbital energies of EH n as a function of the HEH bond angle, and its influence on the structure of EH n as a function of the number of valence electrons.

3. Be able to account for the bonding in organic hydrocarbons in terms of the frontier orbitals of CR, CR2 , and CR3