A deeper look 4 The energy of the bonding

molecular orbital of H2+

E S k
The goal is to calculate the energy of the σ orbital of the  1s
   
hydrogen molecule-ion, written as the linear combination   2
j0  ψBψA
+ ∫ψB − ∇1 − ψAdτ − j0 ∫
2
dτ
ψ+ = N+(ψA + ψB). In general, the energy is the expectation  2me rA1  rB1
value of the hamiltonian operator. Therefore, the energy
E+ of ψ+ is E j
 1s
  
  2
j0  ψ B2 
E+ = ∫ψ +* Hˆψ+ dτ + ∫ψB − ∇1 − ψBdτ − j0 ∫
2
dτ
 2me rB1  rA1 

with the hamiltonian given by eqn 9B.1 and N+ =
1/{2(1 + S)}1/2. Begin by writing a general expression for E +, To see how the integrals give rise to the quantities in red,
and then refine it by recognizing that ψA and ψB are H1s consider the following:
atomic orbitals. • The terms − ( 2 /2me )∇12 − j0 / rA1 and − ( 2 /2me )∇12
Step 1 Write a general expression for the expectation value − j0 / rB1 have the form of the hamiltonian of a hydro-
gen atom (Topic 8A). Because in this case ψA and ψB
Begin by using eqn 9B.1 to write
are H1s orbitals centred on A and B, respectively, it
 2 2  1 1 1 follows that
Hˆψ+ = − ∇1 − j0  + −  ψ+
 2me  rA1 rB1 R  
E ψ
  2 2 j0 j0  j  1s A
 1

= − ∇1 − − ψ+ + 0 ψ+   2
j 
2m r r R
  ∫ψA − 2me ∇1 − rA10 ψA dτ = E1s ∫ψ Adτ = E1s
e A1 B1 2 2

where j0 = e2/4πε0. Because the wavefunction is real, the

expectation value of the hamiltonian is
E ψ
 1s B
  1

E+ = ∫ψ+ Hˆψ+ dτ   2
j 
∫ψB − 2me ∇1 − rB10 ψB dτ = E1s ∫ψ Bdτ = E1s
2 2

Evaluated in step 2 Evaluated in step 3

 
  2 2 j0 j0  j 
= ∫ψ+ − ∇1 − − ψ+ dτ + ∫ψ+  0  ψ+ dτ E ψ
 2me rA1 rB1   R  1s B
  S
 

  2
j 
∫ψA − 2me ∇1 − rB1 ψB dτ = E1s ∫ψAψBdτ
2 0

Step 2 Evaluate the first term

With ψ+ = N+(ψA + ψB), and after some algebra, the first 
E ψ

1s A
S
 

term in the expression from Step 1 expands to   2
j0 
∫ψB − 2me ∇1 − rA1 ψA dτ = E1s ∫ψBψAdτ
2

  2 2 j0 j0 
∫ψ + − 2m ∇1 − r − r ψ+ dτ
 e A1 B1 

where E1s is the energy of the H1s orbital, and S is the

  2 2 j0 j0 
= N +2 ∫ (ψA +ψB ) − ∇1 − − (ψA +ψB )dτ overlap integral.
 2me rA1 rB1 
• Because the atoms are identical
E j
       ψ A2 ψ2
1s

 j0 ∫ dτ = j0 ∫ B dτ = j and
= N  ψ −  ∇ 2 − j0 ψ dτ − j ψ A dτ
2 2
2
rB1 rA1
 ∫ A  2me 1 rA1  A 0∫
+
rB1
ψ Aψ B ψ ψ
j0 ∫ dτ = j0 ∫ B A dτ = k
rA1 rB1
E S k
 1s
   
  2
j  ψAψB
+ ∫ψA − ∇1 − ψBdτ − j0 ∫
2 0
dτ
 2me rB1  rA1
2 A deeper look 4 The energy of the bonding molecular orbital of H +2

Therefore, in terms of the parameters E1s, S, j, and k, the Step 4 Combine the expressions from Steps 2 and 3
first term simplifies to Because H1s orbitals were used to arrive at the result in
Step 2, write E+ = E σ, the energy of the σ molecular orbital
  2 2 j0 j0 
∫ − 2me ∇1 − rA1 − rB1 ψ +dτ = 2N + {E1s (1+ S )− ( j + k)}
ψ and
2
+
From Step 3
  
From Step 2
2 j
Step 3 Evaluate the second term Eσ = 2 N + {E1s (1+ S )− ( j + k )} + 0
R
The second term in the expression from Step 1 is the With N+ = 1/{2(1 + S)}1/2, it follows that
contribution to the energy from the repulsion between
nuclei. Because j0/R is a constant and the wavefunction is 2 N+2

normalized, that term simplifies to 1 j j + k j0
Eσ = {E (1+ S )− ( j + k )} + 0 = E1s − +
(1+ S ) 1s R 1+ S R
1

j
  j j as in eqn 9B.4.
∫ψ +  R0  ψ +dτ = R0 ∫ψ +dτ = R0
2