PHY 491: Atomic, Molecular, and Condensed Matter Physics

Michigan State University, Fall Semester 2012

Solve by: Wednesday, September 12, 2012

Homework 2 – Solution
2.1. Calculate the ground state energy of a hydrogen atom using the variational principle. Assume that
the variational wave function is a Gaussian of the form
r 2
N e− ( α ) ,

where N is the normalization constant and α is a variational parameter. How does this variational energy
compare with the exact ground state energy?

You will need these integrals:

Z ∞ Z ∞ √ Z ∞ √
−x2 1 2 −x2 π 4 −x2 3 π
xe dx = ; x e dx = ; x e dx = .
0 2 0 4 0 8

Solution:

< ψ(α)|H|ψ(α) >

E(α) = = min.
< ψ(α)|ψ(α) >
Use 2
Z ∞ 2
r r
ψ = N e−( α ) and < ψ|ψ >= 4πN 2 e−2( α ) r2 dr .
0
√
Change variable to x = 2 αr to get for the denominator
3 Z ∞
α α3 √

2
< ψ(α)|ψ(α) >= 4πN 2 √ x2 e−x dx = 4πN 2 √ π .
2 0 8 2
In the numerator, we consider the kinetic and the potential part separately. For the kinetic part, we get
1
Z
< ψ(α)|T |ψ(α) > = − ψ ∗ ∇2 ψ dr
~
2
Z ∞
1 1 d 2 d −( r )2
 
r 2
2 2 −( α )
= − 4πN r dre r e α
2 0 r2 dr dr
!
4π 2 ∞ 2r4
Z
r 2
= − 2N 3r2 − 2 e−2( α ) dr .
α 0 α
√
Change the variable again to x = 2 αr to obtain

α 3
5 Z ∞
12πN 2 8πN 2
 Z ∞
α
 
2 2
< ψ(α)|T |ψ(α) > = √ x2 e−x dx − √ x4 e−x dx
α2 2 0 α4 2 0
√
6 π
= 4πN 2 α √ .
32 2
Consequently,
< ψ(α)|T |ψ(α) > 3
= .
< ψ(α)|ψ(α) > 2α2

1
Similarly,
Z ∞
r 2 1
< ψ(α)|V |ψ(α) > = −4πN 2 r2 e−2( α ) dr
0 r
α 2
  Z ∞
2
= −4πN 2
√ xe−x dx
2 0
!
α 2
= −4πN 2 .
4

Thus, r
< ψ(α)|V |ψ(α) > 1 8
=− .
< ψ(α)|ψ(α) > α π
Combining all our results, the trial energy (variational energy) is
r
3 81
E(α) = − .
2α2 πα
Minimizing the trial energy with respect to the variable α, we get
r
π
amin = 3
8
and
4 8 4
Emin = − =− Hartree = −11.54 eV .
3π 3π 3π
This is about 2 eV higher than the exact energy. Not bad!

~ >and show that for the hydrogen atom

2.2. Use the virial theorem which states that 2 < T >=< ~r · ∇V
1 1
< ψnlm | |ψnlm >= 2 .
r n aB

Solution:
* +
e2
2 < T >=< ~r·∇V >= r 2 =−<V > .
r

For the nth energy level,

1
En = < T >n + < V >n = + < V >n
* + 2
1 e2 me4
= − =− 2 2 .
2 r n 2h̄ n

Substituting
h̄2
aB =
me2
we get
1 1 1
 
< ψnlm | |ψnlm >= = .
r r n n2 aB

2
2.3. Use the Hellmann-Feynman theorem, which states that
∂En ∂H
=< ψn | |ψn >
∂λ ∂λ
to show that for a hydrogen atom
1 1
< ψnlm | |ψnlm >= 2 ,
r n aB
1 1
< ψnlm | 2 |ψnlm >= .
r (l + 12 )n3 a2B

Solution:

1 1
< ψnlm | |ψnlm >= 2
r n aB

has been worked out in Class using the Hellmann-Feynman theorem and e2 = λ as a parameter. So we
only need to prove
1 1
< ψnlm | 2 |ψnlm >= 1 .
r (l + 2 )n3 a2B
After separating the radial and angular parts, the effective Hamiltonian for the hydrogen atom can be
written as
h̄2 1 d 2 d l(l + 1) e2
 
H=− r − − ≡H(l) .
2m r2 dr dr r2 r
The Hellmann-Feynman theorem gives

∂H(l) ∂Enl
< ψnl | |ψnl > = ,
∂l ∂l " # " #
h̄2 1 ∂ me4 ∂ me4
 
(2l + 1) 2 = − =−
2m r nl ∂l 2h̄2 n2 ∂l 2h̄2 (jmax + l + 1)2
" #
me4 me4
= = .
h̄2 (jmax + l + 1)3 h̄2 n3

1 1 1
 
< ψnlm | |ψnlm >= = .
r2 r2 nl (l + 12 )n3 a2B

(1) (1)
2.4. Using the first order perturbation results for Emv , where mv denotes mass-velocity, and for Eso ,
where so denotes spin-orbit, show that
!
(1) (1) (1) (En0 )2 4n
Emv + Eso = Ef s = 3− ,
2mc2 j + 12

where f s denotes fine structure and j is the total angular momentum containing orbital angular momen-
tum plus spin.

3
Solution:

" #
(E 0 )2 4n
(1)
Emv = − n2 −3
2mc l + 21
3
" #
(E 0 )2 j(j + 1) − l(l + 1) −
(1)
Eso = − n2 n 4
.
mc l(l + 21 )(l + 1)

(1)
Adding the two expressions we obtain Ef s . Since s = 1/2, we have j = l + 1/2 or j = l − 1/2. This
means that l = j − 1/2 or l = j + 1/2. Eliminate l from the above equation for each value of l. Do the
algebra and you will get the answer in terms of j.