PH 422: Quantum Mechanics II

Tutorial Sheet 3
This tutorial sheet contains problems related to the use of variational principle in quan-
tum mechanics.

1. Obtain the energy of the ground state of a one-dimensional (1D) simple-harmonic

−αx2
oscillator (SHO) using the trial wave function ψ(x) = ce , where c is the normal-
ization constant, and α is the variational parameter.
Soln: Let us estimate the ground state of one-dimensional simple harmonic oscillator
2
using the trial wave function of the form ψ(x) = ce−αx Because this function is of the
form exact wave function, the obtained energy should be exact ground state energy
~ω
. Let us rst normalize ψ(x)
2
Z ∞
2
hψ|ψi = c 2
e−2αx dx = 1
−∞
√
Substitute t = 2αx
∞
r
c2
Z
−t2 π
⇒ hψ|ψi = √ e dt = c2 =1
2α −∞ 2α
 2α 1/4
⇒c=
π
R∞ 2 √
Above we used value of the Gaussian integral
−∞
e−t dt = π .Now
r ∞
hψ|H|ψi ~2 d2 −αx2 1
Z
2α 2

2 2 −αx2

E(α) = = e−αx − e + mω x e dx
hψ|ψi π −∞ 2m dx2 2

Now

d2  −αx2 d −αx2


e = − 2αxe
dx2 dx !
−αx2 −αx2
= − 2αe + 4α2 x2 e

r ∞
~2 d2 −αx2 1
Z
2α 2

2 2 −αx2

⇒ E(α) = e−αx − e + mω x e dx
π −∞ 2m dx2 2
Using the standard integral

Z ∞ √ a2n+1 (2n − 1)!

x2
x2n e− a2 dx = π
−∞ 2n

We have √ 
Z ∞
2 −2αx2 π 1 3
xe dx = √
−∞ 2 2α

1
 So that
(r r r √ √ √ )
2απ ~2 ~2 2α 2 π 1 1 2 π 2α
E(α) = 2α − 4α + mω √
π
2α 2m 2m π 2 (2α)3/2 2 2 π (2α)3/2
( )
~2 mω 2
E(α) = α+
2m 8α

dE ~2 mω 2
=0⇒ − =0
dα 2m 8α2
mω
⇒α=
2~

~2 mω mω 2 mω
⇒ Emin = + ×
2m 2~ 8 2~
~ω ~ω ~ω
Emin = + =
⇒ 4 4 2
= E0 (Exact GS)
and
 mω 1/4 mωx2
ψ(x) = e− 2~
π~
= ψ0 (x)
Thus, as expected, we recover the exact ground state energy and wave function for
this trial wave function

2. In the variational principle as applied to quantum mechanics, one minimizes the inte-
~2 ∗ 2
ψ ∇ ψ+V ψ ∗ ψ}d3 r, subject to the normalization condition
R
gral I
R ∗ = hψ|H|ψi = {− 2m
ψ ψd3 r = 1. Show using integration by parts, that one can also use the expression
R ~2
I = { 2m ∇ψ ∗ · ∇ψ + V ψ ∗ ψ}d3 r.
Soln:
~2 ∗ 2
Z  
∗
I= − ψ ∇ ψ + V ψ ψ d3 r
2m
The second term remains unchanged so we concentrate only on the rst term

~2
Z
I1 = − ψ ∗ ∇2 ψd3 r
2m
Z ∞Z ∞Z ∞
~2
 2
∂ ψ ∂ 2ψ ∂ 2ψ

∗
=− ψ + 2 + 2 dxdydz (1)
2m −∞ −∞ −∞ ∂x2 ∂y ∂z
Let us consider the rst integral and apply integration by parts
Z ∞Z ∞Z ∞
~2 ∂ 2ψ
I1x =− ψ ∗ 2 dxdydz
2m −∞ −∞ −∞ ∂x
Z ∞ Z ∞ Z ∞Z ∞Z ∞
~2 ∂ψ ∗ ∂ψ

∞
∗ ∂ψ
=− dy dzψ − dxdydz
2m −∞ −∞ ∂x −∞ −∞ −∞ −∞ ∂x ∂x

2
 the rst term on the RHS vanishes because ψ ∗ (x = ±∞, y, z) = 0, because wave func-
tion (and its complex conjugate) must vanish at innity for it to be normalizable

~2 ∂ψ ∗ ∂ψ
Z Z Z
I1x = dxdydz (2)
2m ∂x ∂x
Similarly we can show
Z ∞Z ∞Z ∞
~2 ∂ 2ψ
I1y = − ψ ∗ 2 dxdydz
2m −∞ −∞ −∞ ∂y
(3)
~2 ∂ψ ∗ ∂ψ
Z Z Z
= dxdydz
2m ∂y ∂y
and Z ∞Z ∞Z ∞
~2 ∂ 2ψ
I1z = − ψ ∗ 2 dxdydz
2m −∞ −∞ −∞ ∂z
(4)
~2 Z Z Z
∂ψ ∗ ∂ψ
= dxdydz
2m ∂z ∂z
using Eq.(2),Eq.(3),Eq.(4) in Eq.(1), we have

~2 ∂ψ ∗ ∂ψ ∂ψ ∗ ∂ψ ∂ψ ∗ ∂ψ
Z  
I1 = + + d3 r
2m ∂x ∂x ∂y ∂y ∂z ∂z
but

∂ψ ∗ ∂ψ ∂ψ ∗ ∂ψ ∂ψ ∗ ∂ψ ∂ψ ∗ ∂ψ ∗ ∂ψ ∗
  
∂ψ ∂ψ ∂ψ
+ + = î + ĵ + k̂ . î + ĵ + k̂
∂x ∂x ∂y ∂y ∂z ∂z ∂x ∂y ∂z ∂x ∂y ∂z
~ ).∇ψ
= (∇ψ ∗ ~

~2
Z
⇒ I1 = ~ ∗ ) · (∇ψ)d
(∇ψ ~ 3
r
2m

3. Estimate the ground state energy of a 1D-SHO using the trial wave function of
−α|x|
form ψ(x) = Ce , treating α as a variational parameter. (Helpful integral:
Rthe
∞ −αx n n!
0
e x dx = αn+1 .)
Soln: First we normalise ψ(x)
Z ∞
c 2
e−2α|x| dx
−∞
Z 0 Z ∞
⇒ c2 e2αx + c2 e−2αx dx = 1
−∞ 0
c2 c2
⇒ + =1
2α 2α √
⇒c= α

3
 √ −α|x|
ψ(x) = αe
∂2ψ
Because the slope of this wave function is discontinuous at
∂x2
x = 0, so
is not dened
there. Therefore, we use expression of Prob. 2 for computing energy expectation value

E(α) = hψ(α)|H|ψ(α)i
Z ∞  2  2 
~ dψ 2
= + V ψ dx
−∞ 2m dx
Z  αx 2 2
~2 α ∞ de−αx
Z ∞
~2 α 0
Z  Z 0
de 1 1
= dx + 2
dx + mω α 2 2αx 2
x e dx + mω α x2 e−2αx dx
2m −∞ dx 2m 0 dx 2 −∞ 2 0

using
Z 0 Z ∞
2!
2 2αx
xe dx = x2 e−2αx dx =
−∞ 0 (2α)3
1
= 3
4α

~2 α3 0 2αx ~2 α3 ∞ −2αx mω 2
Z Z
E(α) = e dx + e dx +
2m −∞ 2m 0 4α2
~2 α3 ~2 α3 mω 2
= + +
4mα 4mα 4α2

~2 α2 mω 2
E(α) = + (5)
2m 4α2
dE ~2 α mω 2
=0⇒ − =0
dα m 2α3

m2 ω 2
⇒ α4 =
2~2 r
1 mω
⇒ α = ± 1/4 (6)
2 ~
1
p mω
but only α= 21/4 ~
will lead to a normalizable wave function, using this in Eq.(5),
we have √
~2 mω mω 2 2~
Emin = × √ + ×
2m ~ 2 4 mω
1 1
Emin = √ ~ω > ~ω
2 2
2
4. Show that for a 1D-SHO, if one uses a trial wave function ψ(x) = cxe−αx ,where c
is the normalization constant and α is the variational parameter, one obtains exact

4
energy E = 23 ~ω of the rst excited state.
Soln: Let us rst normalize the trial wave function

Z ∞
2
c 2
x2 e−2αx dx
−∞

using the result

Z ∞ √ 
2 −2αx2 π 1 3
xe dx = √
−∞ 2 2α
we have above
∞
r
c2
Z
2 π
ψ (x)dx = =1
−∞ 2 8α3
r
√ α3
⇒ c2 = 4 2
π
 3  14
2α
⇒c=2
π

 3  14
2α 2
⇒ ψ(x) = 2 xe−αx
π
 3  14  3  41
dψ(x) 2α −αx2 2α 2
⇒ =2 e −4 αx2 e−αx
dx π π
 2  3  12  3  21  3  12
dψ 2α −2αx2 2α 2 4 −2αx2 2α 2
⇒ =4 e + 16 α xe − 16 αx2 e−2αx
dx π π π

We will use the expression of problem 2 to compute the energy expectation value

E(α) = hψ(α)|H|ψ(α)i
Z ∞  2 Z ∞
~2 dψ 1 2
= dx + mω x2 ψ 2 (x)dx
2m −∞ dx 2 −∞
2
 3 1/2 Z ∞  3 1/2 Z ∞
~ 2α −2αx2 ~2 2α 2
= ×4 e dx + 16α 2
x4 e−2αx dx
2m π −∞ 2m π −∞
2
 3
1/2 Z ∞  3 1/2 Z ∞
~ 2α 2 1 2α 2
− 16α x2 e−2αx dx + mω 2 × 4 x4 e−2αx dx
2m π −∞ 2 π −∞

using the integrals

∞
Z r
−αx2 π
e dx =
−∞ α
and
∞
Z r r
4 −αx2 3!! π 3 π
xe = 2 2 = 2
−∞ 2α α 4α α

5
 we have

1/2 r 1/2 r 1/2 r

2~2 2α3 π 8~2 2α3 8~2 2α3
  
2 3 π 1 π
E(α) = + α − α
m π α m π 4(2α)2 2α m π 2 8α3
1/2 r
2α3

2 2 3 π
+ 2ω m α
π 4(2α)2 2α
2~2 α 8~2 × 3α × α2 8~2 α 2mω 2 × 3α
= + − +
m m × 4 × 4α2 4m 16α2
2 2
3~ α 3mω
= +
2m 8α
3~2 α 3mω 2
E(α) = +
2m 8α
2
dE 3~ 3mω 2
=0⇒ − =0
dα 2m 8α2

m2 ω 2
⇒ α2 =
4~2
mω
⇒α=
2~

mω 3 3
Emin = E(α = ) = ~ω + ~ω
2~ 4 4
3
Emin = ~ω
2
which is exact result

5. Here we derive the linear-combination of basis functions approach, quite commonly

used in quantum mechanics, using a variational principle. Suppose that the Hamilto-
nian of a system is given by H, and we assume that the state ket |ψi corresponding
to its ground state can be approximated as

N
X
|ψi = Cj |ji,
j=1

where |ji denote the known basis kets, while Cj are the unknown expansion coe-
cients which are also the variational parameters in this approach, and, in general, are
complex. In the r representation, the following notation is adopted ψ(r) = hr|ψi, and
φj (r) = hr|ji. Using the variational principle, show that the ground state energy E,
and the state ket |ψi can be obtained by solving the generalized eigenvalue problem

H̃ C̃ = E S̃ C̃,

6
where H̃ and S̃ N × N matrices, representing the Hamiltonian and the
denote the
overlap, with elements dened as Hij = hi|H|ji, Sij = hi|ji, respectively, while Ci
form the N elements of the column vector C̃ , denoting the ground state eigenfunction.
Note that form an orthonormal basis set, hi|ji = δij so that S̃ = I , and the previous
generalized eigenvalue problem reduces to a normal eigenvalue problem.
Soln: According to the variational principle, we should minimize

hψ|H|ψi
E(Ci , Ci∗ ) = ,
hψ|ψi

with respect to the variational coecients Ci , i = 1, 2, 3, . . . N . Using the given

expansion of |ψi, and the denitions of H̃ij = hi|H|ji and S̃ij = hi|ji,we obtain

∗ ∗
P P
∗ hψ|H|ψi j,k C k C j hk|H|ji j,k Ck Cj Hkj
E(Ci , Ci ) = = P ∗
= P ∗
. (7)
hψ|ψi j,k Ck Cj hk|ji j,k Ck Cj Skj

The variational principle in the present case implies that the conditions

∂E
=0
∂Ci
for i = 1, 2, 3, . . . N (8)
∂E
=0
∂Ci∗
∗
must hold. Because Ci 's are complex, therefore, Ci and Ci are independent variables.
∂C ∗ ∂C ∗
∂Ci ∂Ci
Using the results
∂Cj
= ∂Ci∗ = δij and ∂Cij = ∂C ∗ = 0, we obtain on applying Eq. 8 on
j j
Eq. 7

( j,k Ck∗ δij H̃kj )( j,k Ck∗ Cj Skj ) − ( j,k Ck∗ Cj Hkj )( j,k Ck∗ δij Skj )
P P P P
∂E
= = 0.
( j,k Ck∗ Cj Skj )2
P
∂Ci

This can be written as

P ∗  P C∗C H  P
( k Ck∗ Ski )
j kj
∂E ( k Ck Hki ) − Pj,k Ck∗ Cj Skj
j,k k
= =0
( j,k Ck∗ Cj Skj )
P
∂Ci
!
∗
P
X C
j,k k C j H kj X
=⇒ ( Ck∗ Hki ) − P ∗
( Ck∗ Ski ) = 0.
k
C C
j,k k j kj S k

Now, on using Eq. 7 in the second term above, we have

X X
( Ck∗ Hki ) − E( Ck∗ Ski ) = 0. (9)
k k

The complex conjugate of the previous equation yields

X X
∗ ∗
( Ck Hki ) − E( Ck Ski ) = 0.
k k

7
 ∗ ∗
Using the fact that H̃ and S̃ are Hermitian matrices, we have Hki = Hik and Ski = Sik .
On substituting these in previous equation, we obtain
X X
Hik Ck = E Ski Ck
k k

=⇒ H̃ C̃ = E S̃ C̃. (10)

This equation is called a generalized eigenvalue problem because of the presence of the
overlap matrix S̃ on the RHS, and clearly reduces to the normal eigenvalue problem
H̃ C̃ = E C̃ , for an orthonormal basis (S̃ = I ). Note that we obtained this equation by
taking the complex conjugate of the original equation 9, which actually is an eigenvalue
∗ †
problem for the complex conjugates of the coecients, Ck or C̃ (i.e., for hψ|). You can
∂E
verify that if we start with the condition
∂Ci∗
= 0, we will directly get the eigenvalue
problem of Eq. 10.

6. This problem is a simple application of the linear-combination of basis functions ap-

proach. Suppose the wave function of a given quantum mechanical system can be
expanded in terms of three basis functions {|ii, i = 1, 2, 3}, which form an orthonor-
mal set hi|ji = δij . Dening the Hamiltonian matrix elements with respect to these
basis functions as Hij = hi|H|ji, it is given that the only non-zero Hamiltonian matrix
elements are H12 = H21 = H23 = H32 = H13 = H31 = t, where t is a real positive
number. Obtain the eigenvalues and eigenvectors of this Hamiltonian. How do the
results change when we set H13 = H31 = 0?
Soln:

(a) With
 
0 t t
H = t 0 t
t t 0
the characteristic polynomial is

−λ t t
t −λ t = 0
t t −λ

⇒ −λ λ2 − t2 + t t2 + tλ + t t2 + tλ = 0

⇒ 2t2 (t + λ) − λ(λ − t)(λ + t) = 0

⇒ (λ + t) 2t2 − λ2 + λt = 0

⇒ λ = −t
or

⇒λ2 − λt − 2t2 = 0
⇒λ2 − 2λt + λt − 2t2 = 0
⇒λ(λ − 2t) + t(λ − 2t) = 0
⇒(λ + t)(λ − 2t) = 0
⇒λ = −t, λ = 2t

8
 ⇒λ = −t degenerate

λ = 2t

Let's nd the eigenvectors

(i) λ = −t
(H −
 λI)c
 = 0
t t t c1
⇒  t t t   c2  = 0
t t t c3
⇒ c1 + c2 + c3 = 0
Two possibilities

1
1
|λ = −ti1 = √  0 
2 −1
 
1
1
|λ = −ti2 = √  −2 
6 1
(ii) λ = 2t
 (H − λI)c=0 
−2t t t c1
⇒  t −2t t   c2  = 0
t t −2t c3
⇒ −2c1 + c2 + c3 = 0
c1 − 2c2 + c3 = 0
c1 + c2 − 2c3 = 0
Any two of these equations are linearly independent. A possible solution which
orthogonal to |λi1 and |λi2 is
 
1
1
|λ = 2ti3 = √  1 
3 1

(b) When H13 = H31 = 0, we have

 
0 t 0
H = t 0 t
0 t 0

|H − λI| = 0 is
−λ t 0
t −λ t = 0
0 t −λ

9
 ⇒ −λ λ2 − t2 + t2 λ = 0

⇒ λ(λ2 − 2t2 ) = 0
√
⇒ λ = 0, ±t 2

Let's nd the eigenvectors

(i) λ = 0
 (H −  λI)c
 = 0
0 t 0 c1
⇒  t 0 t   c2  = 0
0 t 0 c3
⇒ c2 = 0
c1 + c3 = 0
 
1
1
|λ = 0i = √  0 
2 −1
√
(ii) λ = ± 2t

√ (H − λI)c = 0
  
∓ 2t t √ t c1
⇒  t ∓ 2t t √   c2  = 0
t t √ ∓ 2t c3
⇒ ∓ √ 2c1 + c2 = 0
c1 ∓ 2c √2 + c3 = 0
c2 ∓ 2c3 = 0
Possible solutions are  
√ 1
√
1
|λ = 2ti =  2 
2
1
 
√ 1
√
1
|λ = − 2ti =  − 2 
2
1
We note that in this case, eigenvalues are symmetrically placed about λ = 0,
which is a sign of particle hole symmetry.

7. Estimate the ground state energy of a particle of mass m in a box with V = 0, for
0 ≤ x ≤ a, and V = ∞, otherwise, using variational principle. For the purpose, take
a wave function consisting of two linear components ψ1 (x) and ψ2 (x) dened by: (i)
ψ1 (0) = 0, ψ1 (x = α) = C for 0 ≤ x ≤ α, and (ii) ψ2 (x = α) = C, ψ2 (x = a) = 0, for
α ≤ x ≤ a, where C is the normalization constant, and α is the variational parameter.
Soln: We estimate the ground state energy of a particle of mass m, in a one dimen-
sional box of length a. We consider the trial function to be a linear function which is
zero at x=0 and x=a, and is peaked at x=α, 0 ≤ α ≤ a, where α is the variational
parameter.

10
Clearly

Nx
ψ(x) = ψ1 (x) = f or 0 ≤ x ≤ α
α
N (a − x)
ψ(x) = ψ2 (x) = f or α ≤ x ≤ a
(a − α)
ψ(x) = 0 elsewhere
To obtain normalization constant
a
N2 α 2
Z a
N2
Z Z
2
ψ (x)dx = 2 x dx + (a − x)2 dx
0 α 0 (a − α)2 α
N2 N2
= α+ (a − α) = 1
3 3

N2
a=1
3 r
3
N=
a
r
3x
⇒ ψ1 (x) =
aα
r
3 (a − x)
ψ2 (x) =
a (a − α)
Now the standard form

~2 2
Z
ψ∗ −

E = hψ|H|ψi = ∇ + V ψdτ
2m
is not valid here because ψ 0 (x) is discontinuous at x = α. For such cases one uses the
alternative expression

 ~2
Z
E= (∇ψ ~
~ ∗ ).(∇ψ) + V ψ ∗ ψ dτ
2m

11
which can be obtained by integrating by parts the rst term and using the fact that
∗
the wave function vanishes at innity.For the present case ψ = ψ and V = 0, so that
Z a  2
~2 dψ
E(α) = dx
2m 0 dx
Z α Z a
~2 dψ1 2 ~2 dψ2 2
= dx + dx
2m 0 dx 2m α dx
or
Z α Z a
~2  3  1 ~2  3  1
E(α) = dx + dx
2m a α2 0 2m a (a − α)2 α
~2  3 n 1 1 o
= +
2m a α a − α

dE ~2  3 n 1 1 o
⇒ = − 2+ =0
dα 2m a α (a − α)2
⇒ a − α = ±α
The only meaningful solution is

a
2α = a ⇒ α =
2
and
~2  3  4 6~2
Emin = × =
2m a a ma2
~2 π 2 5~2
E0 (exact) = 2 ≈ ⇒ Emin > E0
2a m ma2
q
2
If we plot the true ground state wave function ψ0 =
a
sin( πx
a
) along with the ap-

proximate wave function ψ(x) is obtained above, we have

Figure 1: Comparison between the exact and the approximate wave functions

12
 a
We note that α=
2
obtained through variational principle ensures that the variational
a
wave function peaks at the same x = , as an exact wave function.
2

8. Consider the Hamiltonian of a particle moving in a 1D Gaussian potential well H =

p2 2
2m
− V0 e−ax , with V0 and a > 0. Estimate its ground-state energy employing varia-
−αx2
tional principle, with a trial wave function of the form ψ(x) = Ce , with α as the
variational parameter.
Soln: Let us compute

∞  2
~2 dψ
Z  
2
E(α) = + V ψ dx
−∞ 2m dx
2 2α 1/4
ψ(x) = Ce−αx


Here where C= π
was computed in problem 1. Now

 1/4 n
dψ(x) 2α 2
o
= − 2αxe−αx
dx π
so
r ∞ ∞
~2
 Z Z 
2α 2 2 −2αx2 −(2α+a)x2
E(α) = 4α x e dx − V0 e dx
π 2m −∞ −∞
r
~2 2 1
 r r 
2α π π
E(α) = 4α − V0
π
2m 2 (2α)3 2α + a
r
~2 2α
= α − V0
2m 2α + a
With this
√ √
dE ~2 2 2 2α
= − V0 p + V0 =0
dα 2m 2 α(2α + a) 2(2α + a)3/2
( √ )
V0 1 2α ~2
=⇒ p √ − =
(2α + a) 2α (2α + a) 2m
aV0 ~2
=⇒ p =
2α(2α + a)3 2m
4m2 a2 V02
=⇒ 2α(2α + a)3 =
~4
After solving this equation for α, we can obtain the value of ground state energy E(α).

9. Using the trial wave function ψ(r) = Ce−αr , where C is the normalization constant,
and α is the variational parameter, estimate the ground state energy of the hydrogen
atom.
Soln:
ψα (r) = Ce−αr

13
 Z Z ∞
ψα2 (r)d3 r =C 2
4πr2 e−2αr dr = 1
0
Z ∞
⇒ 4πc2 r2 e−2αr dr = 1
0
2!
⇒ 4πC 2 =1
(2α)3
πC 2
=1
α3 r
α3
C=
π
r
α3 −αr
ψ(r) = e
π
The Hamiltonian for the hydrogen atom is

~2 2 e2
H=− ∇ − ,
2m r
so that

E(α) = hψ(α)|H|ψ(α)i
~2 2 e2 2
Z    
= ψα − ∇ ψα − ψα (r) dr
2m r

but

~2 2 ~2 ∂ ~2 ~2 ∂2
   
2 ∂ ∂ ∂
− ∇ =− r − sin θ −
2m 2mr2 ∂r ∂r 2mr2 sin θ ∂θ ∂θ 2mr2 sin2 θ ∂ϕ2

As there is no angular dependence of ψα (r) since the ground state functionis spherically

14
symmetric, so the last two terms give us zero, so we are left with

~2 ∂ e2 2
Z     
2 ∂ψα
E(α) = ψα − r − ψα (r) dr
2mr2 ∂r ∂r r
−αr
α3 ~2 ∂ e2 −2αr
Z     
−αr 2 ∂e
= e − r − e dr
π 2mr2 ∂r ∂r r
−αr Z −2αr
~2 α3 e2 α3
Z   
−αr 1 ∂ 2 ∂e e
=− e 2
r dr − dr
2m π r ∂r ∂r π r
Z −2αr
~2 α3 e2 α3
Z  
−αr 1 ∂ 2 −αr

e
=− e 2
r [−αe ] dr − dr
2m π r ∂r π r
Z −2αr
~2 α4 e2 α3
Z  
−αr 1 ∂ 2 −αr
e
= e r e dr − dr
2m π r2 ∂r π r
Z −2αr
~2 α4 e2 α3
Z  
−αr 1  −αr 2 −αr
 e
= e 2
2re − αr e dr − dr
2m π r π r
Z −2αr
~2 α4 e2 α3
Z  
−αr 1  −αr 2 −αr 2 e
4πr2 dr

= e 2
2re − αr e 4πr dr −
2m π r π r
2~2 α4
Z Z
−αr −αr 2 −αr 3 2
re−2αr rdr


= e 2re − αr e dr − 4α e
m
2~2 α4
 Z Z  Z
−2αr 2 −2αr
= 2 re dr − α r e dr − 4α e 3 2
re−2αr rdr
m

Using the denition of Gamma function

Z ∞
Γ(n + 1)
xn e−ax dx = where a > 0
0 an+1
we obtain

2~2 α4
      
1! 2! 3 2 1!
E(α) = 2 −α − 4α e (11)
m (2α)2 (2α)3 (2α)2
4~2 α4
 
1 1
= 2
− 2 − αe2
m 4α 8α
2 2
~α
= − αe2
2m

dE ~2 α
=0⇒ − e2 = 0
dα m
me2 1
⇒α= 2 = (12)
~ a0

15
 ~2
where a0 = me2
is the Bohr radius. Substituting Eq.(12) in Eq.(11), we get

~2 m2 e4 me4
 
Emin = −
2m ~4 ~2
me4 me4
= − 2
2~2 ~
4
me
=− 2
2~

me4
Emin = −
2~2
This is the exact value of the ground state energy of the hydrogen atom, obtained after
solving the Schrödinger equation.

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