Lecture 28: Heteronuclear Diatomic Molecules The material in this lecture covers the following in Atkins. 14.

7 Heteronuclear diatomic molecules (a) Polar bonds (b)Electronegativity (c) The variation principle (d) Two simple cases

Lecture on-line Heteronuclear diatomic molecules (PowerPoint) Heteronuclear diatomic molecules (PDF) Handout for this lecture

Heteronuclear

diatomic

molecules

A heteronuclear diatomic molecule is a diatomic molecule formed from atoms of two different elements HCl CO

The electron distribution in a covalent bond between the atoms is not evenly shared

Because it is energetically favorable for the electron pair to be closer to one atom than the other
The imbalance results in a polar covalent bond in which the electron pair is hared unequally by the atoms

The bond in HF, for instance, is polar , with the electron pair closer to F.
+

HF

Heteronuclear diatomic molecules Polar Bond In homonuclear In heteronuclear diatomics diatomics the the atomic orbitals from the atomic orbitals two nuclei do not contribute from the two nuclei equally to the molecular contribute equally orbitals : to the molecular orbitals : CH 1sH + CAu 6sAu 1 of HAu := 1 g of H2 : 1 = 1sA + 1sB 2(1 + S) g 2(1 + S)
g of F2 : 1 g =
2p A + 2pB 2(1 + S)

of FI :

CF 2p + CI 5p 2(1 + S)

2p A + 2p B of NP : = u of N2 : 1 = u 2(1 + S)

CN 2p N + CP 3p P 2(1 + S)

Heteronuclear diatomic molecules

The ability of an element to attract electrons is a measure of its :

Electronegativity

Electronegativity

Electronegativity according to Pauling :

A = Electronegativity of A B = Electronegativity of B

A B | = 1 1 0.102 {D(A - B) - D(A - A) - D(B - B) 2 2

AA bond energy AB bond energy BB bond energy

Heteronuclear diatomic molecules

Electronegativity

Electronegativity according to Mulliken :

A = Electronegativity of A
1 A = (IA + Eea ) 2

Electron affinity of A
L arg e value indicates that element is a good electron acceptor

Ionization potential of A
L arg e value indicates that electron is difficult to remove poor electron donor

Heteronuclear

diatomic

molecules

Electronegativity

Heteronuclear

diatomic

molecules

Linear variation

We have for the total energy of the trial wavefunction = CA A + CBB

E =

*Hdv
* dv

* dv =
(C A A +CB B )(C A A + CB B ) dv

2 2 2 2 = (C A A + CB B + 2C ACB A B )dv This energy is optimal if E E = 0 and =0 2 2 2 2 CA CB = C A ( Adv + CB B dv

+2C ACB A B dv We now express the energy in terms of the 1 Overlap S 1 coefficients C A and CB 2 2 = C A + CB + 2C ACB S

Heteronuclear diatomic molecules Linear variation theory *Hdv =

(C A A +CB B )H (C A A + CB B ) dv
2 2 = C A AHAdv + CB B HB dv

+2C ACB AHB )dv

Introducing

A = AHAdv

B = B HB dv b

= AHB dv

* 2 2 H = C AA + CB B + 2C ACB

Heteronuclear diatomic molecules Linear variation theory

E =

*Hdv
* dv

2 2 *H = C AA + CB B + 2C ACB 2 2 * = C A + CB + 2C ACB S

Energy of electron in orbital A : Kinetic energy + attraction energy from both nuclei + repulsion from all other electrons Energy of electron in orbital B : Kinetic energy + attraction energy from both nuclei + repulsion from all other electrons

Always negative stabilizing

Always negative stabilizing

Heteronuclear diatomic molecules Linear variation theory

E =

*Hdv
* dv

2 2 *H = C AA + CB B + 2C ACB 2 2 * = C A + CB + 2C ACB S

Overlap between A and B

Resonance integral represents energy of overlap density S

Heteronuclear diatomic molecules Linear variation theory

E (C A , CB ) =

*Hdv
* dv

* 2 2 H = C AA + CB B + 2C ACB 2 2 * = C A + CB + 2C ACB S

hus
2 2 E (C A , CB )[C A + CB + 2C ACB S ] = 2 + C 2 + 2C C A B A A B B

This energy is optimal if E E = 0 and =0 CA CB

Heteronuclear diatomic molecules Linear variation theory Thus 2 2 E(CA , CB )[CA + CB + 2CACBS] =
2 2 CA A + CB B + 2CACB

We shall now differentiate respect to CA and make use of that for the optimal CA dE(CA , CB ) / dCA = o hus o dE (C A , CB ) 2 2 [C A + CB + 2C ACB S ] + E [ 2C A + 2CB S ] dC A

2C AA + 2CB

r: (A E )C A + ( ES )CB = 0

Heteronuclear diatomic molecules Linear variation theory hus

2 2 E (C A , CB )[C A + CB + 2C ACB S ] = 2 + C 2 + 2C C A B A A B B

We shall now differentiate respect to CB and make use of that for the optimal CB dE(CA , CB ) / dCB = o hus o dE (C A , CB ) 2 2 [C A + CB + 2C ACB S ] + E [ 2CB + 2C AS ] dCB

2CB B + 2C A

r: (B E )CB + ( ES )C A = 0

Heteronuclear diatomic molecules Linear variation theory We have derived : Our secular equation (A E )C A + ( ES )CB = 0 reads ( ES )C A + (B E )CB = 0 A - E - ES This is a homogeneous =0 - ES B - E linear equation in the
unknown CA and CB
Homogeneous eq : A11x + A12y = 0 A21x + A22y = 0

This gives us a quadratic equation in E from which we can determine the two roots E+ and E-

Has only solutions if the secular determinants : Here E+ corresponds to the orbital of lower energy A11 A12 and E- to the orbital of higher =0 A21 A 22 energy

Heteronuclear diatomic molecules Linear variation theory

A substitution of E = E+ into the secular equation (A E )C A + ( ES )CB = 0 ( ES )C A + (B E )CB = 0

A substitution of E = E- into the secular equation ( A E)CA + ( ES)CB = 0 ( ES)CA + (B E)CB = 0

affords the coefficients + C+ and CB A

affords the coefficients C- and CB A

We thus obtain the orbital - = CA A + CBB with energy E-

We thus obtain the orbital + + + = CA A + CBB with energy E+

Heteronuclear diatomic molecules Linear variation theory

- = C A A + CB B

E
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 ||

The solutions

1 1 - = A + B 2 2

E = B 1 S
A

A + E+ = 1+ S
B A

1 1 + = A + B 2 2

Heteronuclear diatomic molecules

Linear variation theory

|| 2. A << B or << 1 | A B |
= B + ( SB ) A A B

The solutions

( SB )2 2 E = B B A B A B
+ A

( S A )2 2 E+ = A + A + A B A B

B A

( S A ) + = A + B A B

Heteronuclear diatomic molecules

Linear variation theory The general solution

= 1 2|| arctan 2 B A

= B sin + A cos

E = A cot
A

E + = B + cot

B A

+ = A cos + B sin

Heteronuclear diatomic molecules Linear variation theory

Molecular orbitals og HF

Molecular Orbital Theory Diatomics

Term

symbols

Molecule
HD +

Configuration
(1 )1

Term symbol
2 +

Spin multiplicity
L Tz : 0

2S T + 1

SYM(L z )

Reflection

Molecular Orbital Theory Diatomics

Term

symbols

Molecule

Configuration

Term symbol
+
2 +

HD
HD
2 He3 He

(1 )2
(1 )2 (2 * )1

2s 3s 4 * 2s + 3s
3

(1 )2 (2 *)2
(1 )2 (2 *)2 (3 )2 (1 )2 (2 *)2 (3 )2 (4 *)2

+ + +

LiNa

s 1s
s + 1s

2 *

BeMg

Spin multiplicity
L Tz : 0

2S T + 1

SYM(L z )

Reflection

Molecular Orbital Theory Diatomics

Term

symbols

Molecule Configuration Term symbol

BAl
CSi

(1 )2
(1 )4

3 1 +

1 +

1 + 2 + 1 +

NP +

(5 )1 (1 )4 (5 )2 (1 )4

NP

Spin multiplicity
L Tz : 0

2S T + 1

SYM(L z )

Reflection

Molecular Orbital Theory Diatomics

Term

symbols

Molecule Configuration Term symbol NO SO FCl

(5 )2 (1 )4 (2 *)1 (5 )2 (1 )4 (2 )2
(5 )2 (1 )4 (2 )4
2 3
2 +

6 * 2

Spin multiplicity
L Tz : 0

2S T + 1

SYM(L z )

Reflection

Heteronuclear diatomic molecules

2

Metal - main - group diatomics

2x

2y

Metal

Main group
1x 1y 1

Heteronuclear diatomic molecules

1u

1xg

1yg

Metal - Metal diatomics

1u1

1u2

1g1
1xu

1g2
1yu

1g

What you should learn from this lecture

1. You should be able to construct in qualitative terms the compositions and energies of molecular orbitals for heteronuclear diatomic molecules
2.You should be able to account for how the coefficients changes + + + + in + = CA A + CBB and + = CA A + CBB changes as A becomes more electronegative than B

3. You should know qualitatively how E+ and E- behaves when A and B have the same electronegativity and when A is much more electronegative than B

What you should learn from this lecture 4. You should be able to figure out the electron configuration for maingroup diatomics as well as the term symbol (in simple cases) 5. It would be really cool if you also could account for the bonding in diatomics containing transition metals. But it is not required
6. You are required to be able to derive the equations ( A E)CA + ( ES)CB = 0 ( ES)CA + (B E)CB = 0 However you will not be asked to solve for E or CA and CB in the general case