Quantum Chemistry - Homework

Quantum Problems
Problem 1
In our treatment of the variational theorem, we found that using an adjustable trial wavefunction Ψtrial the
approximate (trial) energy is:
hΨtr |Ĥ|Ψtr i
E=
hΨtr |Ψtr i
which can be used to find the minimum energy as a function of varying Ψtrial . Instead of varying Ψtrial , we
could look at the variation of E as a funciton of somo parameter P . This would give:
dE d
= hΨtr |Ĥ|Ψtr i
dP dP
dΨ∗tr
Z Z Z
∗ dĤ dΨtr
= · Ĥ · Ψtr + Ψtr · · Ψtr + Ψ∗tr · Ĥ ·
dP dP dP
Z ∗ Z Z
dΨint dĤ dΨtr
=E · Ψtr + Ψ∗tr · · Ψtr + E Ψ∗tr ·
dP dP dP
In the above, the trial wavefunction is assumed to be normalized so that the integral in the denominator is
one. From this point, one can show that
dE
= hdĤ/dP i
dP
Show how to get from third equation above to this result. This is the Hellmann-Feynman theorem.
Ans:
From third equation
dΨ∗int
Z Z Z
dĤ dΨtr
E · Ψtr + Ψ∗tr · · Ψtr + E Ψ∗tr ·
dP dP dP
dΨ∗int
Z Z
dΨtr dĤ
=E · Ψtr + Ψ∗tr · + Ψ∗tr · · Ψtr
dP dP dP
Z Z
d dĤ
=E (Ψ∗tr Ψtr ) + Ψ∗tr · · Ψtr
dP dP
As Ψ∗tr Ψtr = 1
Z
dE dĤ dĤ
=⇒ = Ψ∗tr · · Ψtr = h i
dP dP dP
1
Problem 2
For this question, you only need to actually solve anything, just write down what is asked for. The Helium
atom ground state has electronic configuration 1s2 .
a) Write down a Slater determinant that produces an anti-symmetric wavefunciton for the two-electron
system. Remember to include spin and the normalization constant
Ans:
Let α the spin function for the first electron and β the spin function for the second electron. So the Slater
determinant fo the two-electron system is

1 1s(r1 )α(1) 1s(r1 )β(1)
Ψ(r1 , r2 ) = √
2 1s(r2 )α(2) 1s(r2 )β(2)
b) Multiply out the Slater determinant from a) and create the energy correction integrals from the
2
electron-electron interaction Hamiltonian H 0 = 4πe0 r12 . Since both electron are in the 1s spatial state,
you can simplify your integrals using the normalization property of these states, i.e., your integrals need
only include spin.
Ans:
1
Ψ(r1 , r2 ) = √ (1s(r1 )α(1)1s(r2 )β(2) − 1s(r2 )α(2)1s(r1 )β(1))
2
Thus the correction of energy is,
Z
E1 = 1s(r1 )∗ α(2)∗ ĤΨ(r1 , r2 )dr1 dr2
e2 1
Z
1
= 1s(r1 )∗ α(2)∗ √ (1s(r1 )α(1)1s(r2 )β(2) − 1s(r2 )α(2)1s(r1 )β(1)) dr1 dr2
(4π0 ) r12 2
e2
Z
1
=√ |1s(r1 )|2 |α(1)|2 dr1 dr2
2(4π0 ) r12
e2
Z
1
+√ 1s(r1 )∗ α(2)∗ 1s(r1 )∗ α(2)∗
2(4π0 ) r12
c) Your integrals should be of the two types, Coulombic and Exchange. Identify wich is Coulombic and
Exchange integrals.
Ans: The first integral is the Coulombic and the second the Excahnge
3. Recall that the problem for a single particle confined to a ring of fixed radius was solved using the
Hamiltonian
~2 d2 L̂2
Ĥ = − =
2mr2 dφ2 2mr2
This Hamiltonian works just fine for the rotation of a molecule in a vaccum but has to be adjusted in
order to model the rotation if, say, the molecule were rotating in proximity to a solid surface with a
surface charge. Assume that the effect of the surface is to add a potential that varies with the molecular
rotation angle as:
V (φ) = b sin2 φ
in which b is an energy constant. Determine the correction to energy resultanting from this perturbation.
Ans:
2
Firstly we calculate the ground state
~2 d2 L2
Ĥψ(φ) = Eψ(φ) =⇒ − 2 2
ψ(φ) = Eψ(φ) = ψ(φ)
2mr dφ 2mr2
=⇒ ψ(φ) = Ce±imφ
by periodicity and normalization
1
=⇒ ψ(φ) = √ eimφ
2π
Then, the energy correction is
Z
1 1 b b
√ e−imφ b sin2 φ √ eimφ dφ = π=
2π 2π 2π 2
4. Given
~ 0 1
Ŝx =
2 1 0
,
~ 0 −i
Ŝy =
2 i 0
,
~ 1 0
Ŝz = ,
2 0 −1

1
|αi =
0

0
|βi =
1
a) Find matrix forms of Ŝ+ = Ŝx + iŜy and Ŝ− = Ŝx − iŜy .
Ans:

0 1 0 0
Ŝ+ = ~ Ŝ− = ~
0 0 1 0
b) Find Ŝ− |αi; Ŝ+ |αi; Ŝ− |βi; Ŝ+ |βi.
Ans:

0
Ŝ− |αi = ~
1

0
Ŝ+ |αi = ~
0

0
Ŝ− |βi = ~
0

1
Ŝ+ |βi = ~
0
c) An excited state of Helium is 1s(1)α(1)2s(2)α(2). In this state the electron spins are parallel: α(1)α(2).
Given that 2
Ŝ 2 = Ŝ12 + Ŝ22 + 2 Ŝx1 Ŝx2 + Ŝy1 Ŝy2 + Ŝz1 Ŝz2 ,
find Ŝ 2 |α(1)α(2)i. Note that Ŝ1 only operates on electron 1, Ŝz only operates on electron 2, etc.
3
Ans: Explicitly,
2 2
Ŝ 2 = Ŝ12 = Ŝ1 ⊗ I2 + I1 ⊗ Ŝ2 = Ŝ12 ⊗ I2 + 2Ŝ1 ⊗ Ŝ2 + I1 ⊗ Ŝ22
where Ii is the identity operator for the system i and ⊗ is the tensor product. So,
3 2
Ŝi2 = Ŝxi
2 2
+ Ŝyi 2
+ Ŝzi = ~ .
4
Thus,
3 2 3
Ŝ 2 = ~ I1 ⊗ I2 + 2Ŝ1 ⊗ Ŝ2 + ~2 I1 ⊗ I2
4 4
1 h i
= ~2 6I1 ⊗ I2 + 2Ŝ1 ⊗ Ŝ2
4
Then,
~2
Ŝ 2 |α(1)α(2)i = 6|α(1)α(2)i + 2|β(1)β(2)i + 2i2 |β(1)β(2)i + 2|α(1)α(2)i

4
~2
=8|α(1)α(2)i = 2~2 |α(1)α(2)i
4
d) An N electron wavefunction for a ferro magnet will look like: Ψf = α(1)α(2)α(3)α(4)α(5)α(6)...α(N )
with all splin parallel (up, in this case). If this state is an eigenfunction of both Ŝz = Ŝ1z + Ŝ2z + Ŝ3z +
Ŝ4z + Ŝ5z + ... + ŜN z and
2
Ŝ 2 = Ŝ1 + Ŝ2 + Ŝ3 + Ŝ4 + Ŝ5 + ... + ŜN ,
solve for Ŝz |Ψf i and Ŝ 2 |Ψf i

Ans:
Recall, Ŝz |αi = ~ 12 |αi and Ŝ 2 |αi = ~2 12 1

2 + 1 |αi. So,
N
Ŝz |Ψf i = ~ |Ψf i
2
and,
N N
Ŝ 2 |Ψf i = ~2 +1
2 2

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Quantum Problems

solve for Ŝz |Ψf i and Ŝ 2 |Ψf i

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