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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)

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

Electronegativity

Electronegativity

A = Electronegativity of A B = Electronegativity of B

AA bond energy AB bond energy BB bond energy

Electronegativity

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

E =

*Hdv

* dv

* dv =

(C A A +CB B )(C A A + 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

(C A A +CB B )H (C A A + CB B ) dv

2 2 = C A AHAdv + CB B HB dv

Introducing

A = AHAdv

B = B HB dv b

= AHB dv

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

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

E =

*Hdv

* dv

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

Resonance integral represents energy of overlap density S

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

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

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

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

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

- = 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

| 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

|| 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

= 1 2|| arctan 2 B A

= B sin + A cos

E = A cot

A

E + = B + cot

B A

+ = A cos + B sin

Molecular orbitals og HF

Term

symbols

Molecule

HD +

Configuration

(1 )1

Term symbol

2 +

Spin multiplicity

L Tz : 0

2S T + 1

SYM(L z )

Reflection

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

Term

symbols

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

Term

symbols

(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

2

2x

2y

Metal

Main group

1x 1y 1

1u

1xg

1yg

1u1

1u2

1g1

1xu

1g2

1yu

1g

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

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