Lecture 25: Introduction to Molecular Orbital Theory The material in this lecture covers the following in Atkins.

14 Molecular structure Molecular Orbital Theory (a) Linear combinations of atomic orbitals (b) bonding orbitals (c) anti-bonding orbitals

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Molecular Orbital Theory

We shall now discuss ways to approximately solve : He (re , RN ) (re , RN ) = Ee (RN ) (re , RN )
and represent the many - electron wave - function (re , RN )

+ H2

Here He = Te + VNe + Vee + VNN We shall this time use :

Molecular Orbital Theory

+ H2

In valence bond theory we localized one electron to each atom

A B

or

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

el 1.

el 2.

el 2.

el 1.

In molecular orbital theory each electron moves over the whole molecule
A B A B
el 2.

and

el 1.

Both electrons can be on the same nuclei

The two theories are limiting cases (see later) of a more exact theory

Molecular Orbital Theory

We used the orbitals of the one - electron hydrogen to build up wavefunctions for many - electron atoms

+ H2

We shall use the orbitals of the one - electron H+ molecule 2 to describe many electron diatomic molecules

Molecular Orbital Theory

The hamiltonian for the H+ 2 molecule :
1
rB1

+ H2

is given by
h 2 H= e 2me
2

e2 1 4 o rA1

rA1

R B

e2 1 e2 1 + 4 o rB1 4 o R

Kinetic energy of electron Attraction of el. 1 by A Attraction of el. 1 by B

Re pulsion between A and B

+ Molecular Orbital Theory H2 We could now solve : H(r1, R)(r1, R) = E(R)(r1, R)

Where
2

With

e2 1 1 1 h 2 + [ H= e + V(r1, R) V = 4 o rA1 rB1 R 2me

This is possible but tedious

Was first done by a Danish astronomer in 1926 We shall instead find approximate soluions
To this end we write (r1, R) as a linear combination of atomic orbitals (LCAO)

The atomic orbitals are in general those centered on the atoms of our molecule

Molecular Orbital Theory

For H+ that is : 2
r1A / a o

+ H2

rA1

rB1 R B

e 1sA (r1A ) = A(r1A ) = 3 ( ao )3 / 2

e 1sA (r1B ) = A(r1B ) = 3 ( ao )3 / 2

r1B / a o

Where r1A and r1B are related by : r1B = r1A 2 + R2 2r1AR cos We now assume the electron to be equally likely to be on each nuclei and write the molecular orbitals as :

+ (1) = A(1) + B(1)

(1) = A(1) B(1)

Note : we have as many linear combinations as we have atomic orbitals

Molecular Orbital Theory + (1) = A(1) + B(1)

+ H2 (1) = A(1) B(1)

We can normalize our orbitals for easy energy calculation and use in probability density
2 + (1) + (1)dv = N (A(1) + B(1))(A(1) + B(1))dv = 1

2 2 + (1) + (1)dv = N (A(1)A(1)dv + N (B(1)B(1)dv +2 N 2 (A(1)B(1)dv = 1

+2S N2

+ (1) + (1)dv

= =1

+ 1 N2

+ 1 N2

A normalized N =

1 B normalized overlap S > 1 2(1 + S)

Molecular Orbital Theory

+ (1) = A(1) + B(1)

+ H2

(1) = A(1) B(1)

After normalization

+ (1) =

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

1 [A(1) B(1)] 2(1 S)

The electron probability density :

1 + (1) + (1) = [A(1) + B(1)]2 2(1 + S) 1 1 1 2 2 = A(1) + B(1) + 2 AB(1) 2(1 + S) 2(1 + S) 2(1 + S)

Density at A Density at B (Reduced) (Reduced)

Density between A and B (Increased)

Molecular Orbital Theory

+ H2

(a)The amplitude of the bonding molecular orbital in a hydrogen molecule-ion in a plane containing the two nuclei and + (1) =

(b) a contour representation of the amplitude.

1 [A(1) + B(1)] 2(1 + S)

Molecular Orbital Theory

+ H2

A representation of the constructive interference that occurs when two H 1s orbitals overlap and form a bonding orbital. Compare this illustration with Fig.14.14.

+ (1) =

1 [A(1) + B(1)] 2(1 + S)

Molecular Orbital Theory + H2 1 1 1 2 2 (1) = A(1) + B(1) + 2 AB(1) 2(1 + S) 2(1 + S) 2(1 + S)

The boundary surface of a orbital encloses the region where the electrons that occupy the orbital are most likely to be found. Note that the orbital has cylindrical symmetry.

Molecular Orbital Theory

+ H2

The electron density calculated by forming the square of the wavefunction used to construct Fig.14.14. Note the accumulation of electron density in the internuclear region.

1 1 1 2 2 (1) = A(1) + B(1) + 2 AB(1) 2(1 + S) 2(1 + S) 2(1 + S)

+ Molecular Orbital Theory H2 We can now evaluate the energy : E+ = + (1)H(1)+ (1)dv 1 h2 2 e2 1 1 1 (1) = [A(1) + B(1)] H= e + ] + [ 2(1 + S) 2me 4 o rA1 rB1 R 1 E+ = [A(1) + B(1)]H(1)[A(1) + B(1)]dv 2(1 + S) 1 h2 2 1 e2 1 rB1 = ] A(1)[ e ]A(1)dv rA1 2(1 + S) 2me 4 o rA1

h2 2 1 e2 1 + ] B(1)[ e ]B(1)dv 2(1 + S) 2me 4 o rB1

R B

1 e2 1 + ] A(1)[ ]A(1)dv 2(1 + S) 4 o rB1 1 e2 1 + ] B(1)[ ]B(1)dv 2(1 + S) 4 o rA1 h2 2 2 1 1 e2 e2 1 + ] A(1)[ e [ + ]]B(1)dv + 2(1 + S) 2me 4 o rA1 rB1 4 o R

+ Molecular Orbital Theory H2 1 E+ = [A(1) + B(1)]H(1)[A(1) + B(1)]dv 2(1 + S) E1sH h2 2 1 e2 1 = ] A(1)[ e ]A(1)dv 2(1+ S) 2(1 + S) 2me 4 o rA1 E1sH h2 2 1 e2 1 + ] B(1)[ e ]B(1)dv 2(1 + S) 2me 4 o rB1 2(1+ S) 1 e2 1 J + ] A(1)[ ]A(1)dv 2(1 + S) 4 o rB1 2(1+ S) J 1 e2 1 + ] B(1)[ ]B(1)dv 2(1+ S) 2(1 + S) 4 o rA1

h2 2 2 1 1 e2 + ] A(1)[ e [ + ]]B(1)dv 2(1 + S) 2me 4 o rA11 rB1 e 1 + 4 o R

2
rA1

K' (1+ S)

rB1

Molecular Orbital Theory

+ H2

1 ] A(1)A(1)dv 2(1 + S)

J e2 1 1 = ] A(1)A(1)[ ]dv 2(1 + S) 2(1 + S) 4 o rB1

rB1 R

Interaction (attraction) between nucleus B and the charge cloud A(1)A(1)/2(1 + S)

J 1 e2 1 = ] B(1)B(1[ ])dv 2(1 + S) 2(1 + S) 4 o rA1

Interaction (attraction) between nucleus A and the charge cloud B(1)B(1)/2(1 + S)

Molecular Orbital Theory

+ H2

h2 2 2 1 1 e2 ] A(1)[ [ ]]B(1)dv K' = e + 2(1 + S) 2me 4 o rA1 rB1

SE1sH /(1 + S)
h2 2 2 e2 1 = ] A(1)[ e ]]B(1)dv 2(1 + S) 2me 4 o rB1 2 1 ] A(1)B(1)[ ]dv 2(1 + S) 4 o rA1
K
1

rA1

rB1 R B

e2

Interaction (attraction) between nucleus A and the charge cloud A(1)B(1)/(1+ S)

+ Molecular Orbital Theory H2 K - SE1sH E1sH E1sH J J E+ = + (1+ S) 2(1+ S) 2(1+ S) 2(1+ S) 2(1+ S)

e2 1 + 4 o R

E1sH + SE1sH J + K e2 1 E+ = + (1+ S) (1+ S) 4 o R J+K e2 1 E + = E1sH + (1+ S) 4 o R

We get in a similar way that J-K e2 1 + E = E1sH (1- S) 4 o R

Molecular Orbital Theory

+ H2

The calculated and experimental molecular potential energy curves for a hydrogen molecule-ion.

J+K e2 1 E + = E1sH + + (1+ S) 4 o R J-K e2 1 E = E1sH + (1- S) 4 o R

Molecular Orbital Theory

+ H2

(1) =

1 [A(1) B(1)] 2(1 S)

A representation of the destructive interference that occurs when two H1s orbitals overlap and form an antibonding * orbital. Compare this illustration with Fig.14.20.

Molecular Orbital Theory

+ H2

(a) The amplitude of the antibonding molecular orbital in a hydrogen molecule-ion in a plane containing the two nuclei and

(b) a contour representation of the amplitude. Note the internuclear node. 1 (1) = [A(1) B(1)] 2(1 S)

Molecular Orbital Theory

+ H2

1 (1) = A(1)2 + 2(1 S) 1 1 2 B(1) 2 AB(1) 2(1 S) 2(1 S)

The electron density calculated by forming the square of the wavefunction used to construct Fig.14.20. Note the elimination of electron density from the internuclear region.

Molecular Orbital Theory

+ H2

A partial explanation of the origin of bonding and antibonding effects.

+ (1) =

1 [A(1) + B(1)] 2(1 + S)

(1) =

1 [A(1) B(1)] 2(1 S)

(a) In a bonding orbital, the nuclei are attracted to the accumulation of electron density in the internuclear region.

(b) In an antibonding orbital, the nuclei are attracted to an accumulation of electron density outside the internuclear region.

Molecular Orbital Theory

+ H2

A molecular orbital energy level diagram for orbitals constructed from the overlap of H1s orbitals; the separation of the levels corresponds to that found at the equilibrium bond length. The ground electronic configuration of H2 is obtained by accommodating the two electrons in the lowest available orbital (the bonding orbital).

What you should learn from this lecture

Be able to construct the Hamiltonian h2 2 e2 1 e2 1 e2 1 H= e + 2me 4 o rA1 4 o rB1 4 o R

1
rB1

rA1

Understand the justification for constructing the two molecular orbitals as linear combinations of atomic orbitals + (1) = N + (A(1) + B(1)) and (1) = N (A(1) B(1)) and be able to evaluate the normalization constants from the overlap integral S = A(1)B(1)dv You are not asked to derive the energy expressions
J+K e2 1 for + : E + = E1sH + (1 + S) 4 o R J-K e2 1 or - : E = E1sH + (1 - S) 4 o R

R B

What you should learn from this lecture

However you should understand the meening of J = A(1)A(1)[ e2 1 4 o rB1 ]dv and
1
rB1

rA1
A

e2 1 ]dv and undertand how K K = A(1)B(1)[ 4 o rA1 stabilize + and destabalizes .

R B

It is expected that you can derive the expression for the density due to + as : 1 1 1 2+ 2 +2 (1) = A(1) B(1) A(1)B(1) 2(1 + S) 2(1 + S) 2(1 + S) You shoule further understand the meening of A(1)2 , B(1)2 , and A(1)B(1). Also you should understand 1 how + 2 A(1)B(1) influence the energy E+ as well 2(1 + S) as the features of Fig 14.16

What you should learn from this lecture It is expected that you can derive the expression for the density due to - as : 1 1 1 2+ 2 2 (1) = A(1) B(1) A(1)B(1) 2(1 S) 2(1 S) 2(1 S) You shoule further understand the meening of
A(1)2 , B(1)2 , and A(1)B(1). Also you should understand 1 how 2 A(1)B(1) influences the energy E - as well 2(1 S) as the features of Fig 14.21
Unders tan d the features of the plots in Fig. 14.17 and 14.19 for + (1) = N + (A(1) + B(1)) and (1) = N (A(1) B(1)), respectively.

Make note of the potential energy curve in Fig 14.18 and observe that E+ is lowered less in energy (compared to E1s than E- is increased (see also Fig 14.24