Chapter Three

Approximation Method: Correction Theories

The systems that have an exact solution of S.E. are in general

virtual systems, such as potential step, potential well, …..etc. real systems
are almost more complicated, for example;

i. Usually oscillators are not a simple harmonics.

ii. The presence of external forces, such as the electromagnetic fields, will
change the energy levels of an atom.
iii. The mutual interaction between the particles in the more than one
particle system will make S.E. can not be solved.
iv. S.E. can not have an exact solution when spin is taken into
consideration.

Therefore, we need the correction methods.

Time Independent None Degenerate Perturbation Theory:

Rough treatment:

i. Assume that we have a quantum mechanical system described by S.E.

∧
H ψ n = E nψ n
But this equation can not be solved exactly as before, thus we assume that
there is a small (rough) perturbation such that;

∧ ∧ ∧ ′ ∧ ′ ∧
H = Ho+ H H 〈〈 H o
∧
H o ≡ Exact part
∧ ′
H ≡ Perturbed part
∧
Remember that H o U n = EonU n

ii. The effect of the perturbation is;

Eon → Eo U o →ψ o
E1n → E1 U1 →ψ 1
E2 n → E2 U 2 →ψ 2

iii. To calculate roughly the first order correction to Eon, we have to solve
the S.E.;
∧ ∧ ∧ ′
H ψ n = ( H o + H )ψ n = Enψ n
We know;
∧

∫U
*
H U n = EonU n and U n dτ = δ mn
m

For small perturbation;

En ≈ Eon + E1n and ψ n ≈ U n

Then;
 ∧ ∧ ′
H o U n + H U n ≈ EonU n + E1nU n
∧ ′
H U n ≈ E1nU n
Multiply from the left by U m* and integrate
∧ ′ ∧ ′
E1n ≈ ∫ U m* H U n dτ = ( H )nn
Therefore, the first order correction to En is roughly the expectation value
∧ ′
of the perturbed energy ( H ) when the system in state Un.
Formal Treatment
∧ ∧ ∧ ′
Assume; H = Ho+ λ H 0 〈λ 〈1
Where λ is the perturbation factor.
Such that;
λ = 0 Unperturbed
λ = 1 Full perturbed
Let;
ψ n = ψ on + λψ 1n + λ2ψ 2 n + ...........
E n = E on + λE1n + λ2 E 2 n + ...........
∧
H ψ n = E nψ n
∧ ∧ ′
( H o + λ H )(ψ on + λψ 1n + λ2ψ 2 n + ......) = ( E on + λE1 n + λ2 E 2 n + ......)
(ψ on + λψ 1n + λ2ψ 2 n + .....)
( H oψ on − Eonψ on ) + λ ( H ′ψ on + H oψ on − E1nψ on − Eonψ 1n ) +
λ2 ( H ′ψ 1n + ψ oψ 2 n − E2 nψ on − E1nψ 1n − Eonψ 2 n ) + λ3 (........) + ....... = 0

Zero- order correction:

( H oψ on − Eonψ on ) = 0
∴ H oψ on = Eonψ on
But;
H oU n = EonU n

⇒ ψ on = U n

First- order correction:

H ′ψ on + H oψ 1n = E1nψ on + Eonψ 1 n

Assume;

ψ 1n = ∑ ankU k
k
H ′U n + H o ∑ ankU k = E1nU n + Eon ∑ ankU k
k k

Multiply from the left by U m* and integrate over all the system space;

∫U
*
m
H ′U n dτ + ∑ a nk Eok ∫ U m* U k dτ = E1 n ∫ U m* U n dτ + E on ∑ a nk ∫ U m* U k dτ
k k

( H ′ )mn + ∑ a nk E ok δ mk = E1 nδ mn + Eon ∑ a nk δ mk
k k

( H ′ )mn + a nm E om = E1nδ mn + E on a nm
( H ′ )mn + a nm ( E om − E on ) = E1nδ mn

Case i. m = n ⇒ E1n = ( H ′ )mn

Case ii. m ≠ n ⇒ anm = ( H ′ )mn /( Eon − Eom )

ψ 1n = ∑ anmU m
m

= ∑ anmU m + annU n
m≠n

H.w: using the relation ψ = ψ on + λψ 1n , prove that ann = 0 ?

The matrix of H ′ called Matrix of Perturbation;

( H ′ )mn = ∫ U m* H ′U n dτ

( H ′ )oo ( H ′ )o 1 ..... ( H ′ )on 

( H ′ ) ( H ′ )11 ..... ( H ′ )1n 
 1o

 ..... ..... ..... ..... 
 
( H ′ )no ( H ′ )n 1 ..... ( H ′ )nn 

For the first order correction;

En = Eon + ( H ′ )nn Where E1 n = ( H ′ )nn

( H ′ )mn ( H ′ )mn
ψ n = Un + ∑ Um Where ψ 1m = ∑ Um
m ≠ n E on − Eom m ≠ n E on − E om
Notes:

1. First order correction to energy comes from diagonal elements of

the perturbation matrix.
2. First order correction to wave function comes from the off-
diagonal elements of perturbation matrix.
3. Depending on the denominator, states which contribute most to ψ n
will be those for which Eom is closes to Eon.

Second- order correction:

H ′ψ 1n + H oψ 2 n = E2 nψ on + E1nψ 1n + Eonψ 2 n

Recall that ψ 1n = ∑ ankU k and assume that; ψ 2 n = ∑ bnjU j then;

k j

∑a
k
nk
H ′U k + ∑ bnj H oU j = E2 nU n + E1n ∑ ankU k + Eon ∑ bnjU j
j k j

Multiply from the left by U m* and integrate over all space;

∑a
k
nk
( H ′ )mk + ∑ bnj Eojδ mj = E2 nδ mn + E1n ∑ ank δ mk + Eon ∑ bnjδ mj
j k j

∑a
k
nk
( H ′ )mk + bnm Eom = E2 nδ mn + E1n anm + Eon bnm

Case (i): m = n

E2 n = ∑ ank ( H ′ )nk − E1n ann

k

( H ′ )kn
=∑ .( H ′ )nk + ann ( H ′ )nn − E1n ann
k ≠ n Eon − Eok

2
( H ′ )nk
=∑
k ≠ n Eon − E ok

Case (ii): m ≠ n

∑a
k
nk
( H ′ )mk = bnm ( Eon − Eom ) + E1n a nm
 ( H ′ )mk E1 n
∴ bnm = ∑ ank − a nm
k Eon − Eom Eon − Eom

Q ann = 0 and E1n = ( H ′ )nn

( H ′ )kn .( H ′ )mk ( H ′ )mn .( H ′ )nn

∴ bnm = ∑ −
k ≠ n ( Eon − E ok ).( E on − Eom ) ( Eon − Eom ) 2

H.w: show that;

1
∑ ank
2
bnn = −
2 k ≠n
1
∑ anm
2
=−
2 m≠n
2
1 ( H ′ )mn
=− ∑
2 m ≠ n ( Eon − Eom ) 2
ψ 2 n = ∑ bnjU j = ∑ bnjU j + bnnU n
j j≠n

= ∑ bnmU m + bnnU n
m≠ n

 ( H ′ )kn .( H ′ )mk ( H ′ )mn .( H ′ )nn  1 ( H ′ )mn

2

= ∑ ∑ − U m − U n 
m ≠ n   k ≠ n ( E on − E ok )( E on − Eom )
 ( Eon − Eom )  2 ( Eon − Eom )2 

Therefore, the energy and the wave function corrected up to the second-
order are;
2
( H ′ )nk
En = Eon + ( H ′ )nn + ∑
k ≠ n ( Eon − E ok )

ψ n = U on + ∑ anmU m + ∑ bnmU m + bnnU n

m≠n m≠ n

Solution:

∫ψ ψdτ = 1
*
∫ (ψ o
+ λψ 1 + λ2ψ 2 )* .(ψ o + λψ 1 + λ2ψ 2 )dτ = 1

ψ o*ψ o + λψ o*ψ 1 + λ2ψ o*ψ 2 + λψ 1*ψ o + λ2ψ 1*ψ 1 + λ3ψ 1*ψ 2 + λ2ψ 2*ψ o + 
∫ λ3ψ *ψ + λ4ψ *ψ dτ = 1
 2 1 2 2 

U on* U on + 
 
∫ λU on* ∑ anmU m + λ2U on* ∑ bnjU j + λ ∑ a*nmU m* U on + λ2 ∑ anm 2 U m* U m + λ2 ∑ bnj* U *jU on dτ = 1
 m j m m j


1 + λ ∑ a nmδ nm + λ2 ∑ bnjδ nj + λ ∑ a *nmδ mn + λ2 ∑ a nm δ nm + λ2 ∑ bnj* δ jn = 1

2

m j m m j

1 + λa nn + λ2 bnn + λa *nn + λ2 ∑ a nm + λ2 bnn* = 1

2

Q a nn = a *nn = 0

∴ 1 + λ2 bnn + λ2 ∑ a nm + λ2 bnn* = 1
2

Q bnn = bnn*

∴ 1 + λ2 ( 2bnn + ∑ a nm ) = 1
2

1
∑
2
⇒ bnn = − a nm , a nn = 0
2 m≠n

Notes:

1. Second order correction to energy involves first order correction to

wave function.
2. Second order correction to energy is smaller by ( H ′ )nk /( Eon − Eok )
than the first order.
3. Perturbation wave function rapidly get very complicated.
4. In principle we have a method to proceed to higher order correction
as needed.
Stark Effect on S.H.O.:
b

V = − ∫ E cos θdx = − Ex
a

energy = −eV = eEx

∧ 2
p 1
H = x + mω 2 x 2 − eEx
2m 2
∧ 2
px 1
Ho = + mω 2 x 2 and H ′ = −eEx
2m 2

First order correction to energy: E1n = ( H ′) nn = (−eEx)nn = ?

Second order correction:
2
( H ′ )nk
E2 n = ∑
k ≠ m E on − Eok

+∞

( H ′ )nk = −eE ∫ U n* xU k dx
−∞

−1 ∧+
x = (2α ) 2 ( aˆ + a ) ,α = mω / h

− eE
+∞ ∧ ∧+
∫
*
∴ ( H ′) nk = U n (a + a )U k dx
2α −∞

eE
=−
2α
{ kδ n ,k − 1 + k + 1δ n ,k + 1 }
Thus the only non- zero matrix elements of ( H ′ )nk are those in which
k = n + 1 and k = n − 1 , so;

0 1 0 ..... .....
 .....
eE 1 0 2 .....

( H ′ )nk = −
2α 0 2 0 3 .....
 
0 0 3 0 .....
 2
( H ′ )nk
E2 n = ∑
k ≠ m E on − Eok

e2E 2  n +1 n 
=  + 
2α  (−hω ) hω 
e2 E 2
E2 n = −
2 mω 2
1 e2 E 2
∴ En = ( n + )hω −
2 2mω 2

hω e 2 E 2 / 2 mω 2

hω

Hence, the effect of the perturbation is to shift each energy level by a

mount − e 2 E 2 / 2mω 2 .

Anharmonic Oscillator:

Oscillators are the basis of many important models in physics, for

examples (photons, phonons, magnons,…..). In real system, it is often
necessary to employ an anharmonic oscillator with cubic and / or
quadratic terms in the potential energy.

∧ 2
∧2 ∧3 ∧4
∧
px 1
H= + mω 2 x + c x + D x
2m 2
Let H ′ = cx 3 only.
∧
p x2 1
H= + mω 2 x 2 + cx 3
2m 2
E1n = ( H ′ )nn = ∫ U n* cx 3U n dx = zero

Off diagonal:
( H ′ )nk = ∫ U n* H ′U k dx = c 〈 n \ x 3 \ k 〉

−3 ∧ ∧+
x 3 = ( 2α ) 2 ( a + a )3
−3 ∧3 ∧ ∧+ ∧ ∧+ ∧ ∧+ ∧ +3
= ( 2α ) 2 ( a + 3 a a a + 3 a a a + a )
 ∧3 ∧ ∧+ ∧ ∧+ ∧ ∧+ ∧ +3 
2 〈 n | a
−3
∴ ( H ′) nk = c(2α )  | k 〉 + 3〈 n | a a a | k 〉 + 3〈 n | a a a | k 〉 + 〈 n | a | k〉
 
First term:
∧∧∧ ∧∧
〈 n | a a a | k 〉 = k 〈 n | a a | k − 1〉
∧
= k k − 1〈 n | a | k − 2〉

= k k − 1 k − 2 〈 n | k − 3〉

= k ( k − 1 )( k − 2 )δ n ,k − 3

Second term:
∧ ∧+ ∧ ∧ ∧+
3〈 n | a a a | k 〉 = 3 k 〈 n | a a | k − 1〉
∧
= 3 k k 〈n | a | k 〉

= 3 k k k 〈 n | k − 1〉

= 3 k k δ n ,k − 1

Third term:
∧+ ∧ ∧+ ∧+ ∧
3〈n | a a a | k 〉 = 3 k + 1〈n | a a | k + 1〉
∧+
= 3 k + 1 k + 1〈 n | a | k 〉

= 3 k + 1 k + 1 k + 1〈 n | k + 1〉

= 3( k + 1 ) k + 1δ n ,k + 1

Forth term:
∧+ ∧+ ∧+ ∧+ ∧+
〈 n | a a a | k 〉 = k + 1〈 n | a a | k + 1〉
 ∧+
= k + 1 k + 2 〈n | a | k + 2〉

= k + 1 k + 2 k + 3 〈 n | k + 3〉

= ( k + 1 )( k + 2 )( k + 3 )δ n ,k + 3
 k (k − 1)(k − 2)δ n,k −3 + 3k k δ n,k −1 + 3(k + 1) k + 1δ n,k +1 + 
2
−3
∴ ( H ′) nk = c(2α )  
 (k + 1)(k + 2)(k + 3)δ n,k +3 

0 3 0 6 0 0 .....
 
 3 0 6 2 0 2 6 0 .....
−3  0 6 2 0 9 3 0 2 15 .....
= c(2α ) 2  
 6 0 9 3 0 24 0 .....
0 2 6 0 24 0 15 5 .....
 
..... ..... ..... ..... ..... 0 .....

Note that all the diagonal matrix element are equal to zero as will be
found before.

Perturbed Energies:
En = Eon + E1n + E2 n
2
( H ′ )nk
= Eon + ( H ′ )nn + ∑
k ≠ m Eon − Eok

For ground state (n=0):

2
( H ′ )ok
Eo = Eoo + ( H ′ )oo + ∑
k ≠ o Eoo − E ok

The only non- zero elements are; ( H ′ )o 1 and ( H ′ )o 3 which equal to

−3 −3
3c( 2α ) 2
and 6 c( 2α ) 2
respectively.

 
1 c  3 2 2
( 6) 2

∴ Eo = hω + 0 +  + 
2 8α 3  1 hω − 3 hω 1 hω − 7 hω 
2 2 2 2 
 1 11 c 2
= hω −
2 8 hωα 3

Perturbed wave functions:

ψ n = ψ on + ψ 1n + .......

Ground state (n=0):

( H ′ )ko
ψ o = Uo + ∑ Uk
k ≠ o E oo − E ok

c  2 
= Uo − 3 3U 1 + U3 
( 2α ) 2 hω  3 
Time- Independent Degenerate Perturbation Theory:

1. Degenerate quantum system: two or more wave function has the

same energy.
2. first order correction are found as in the form: E1n = ( H ′ )nn .
3. If the first order corrections are non- zero, they may lift the
degeneracy. For example, application of uniform magnetic field to
hydrogen atom (Zeeman Effect) gives different values of the
magnetic quantum number (m). While application of the electric
field (Stark Effect) does not lift the degeneracy in first order
because E1n=0.
4. We can not use the second order perturbation theory because of the
denominator term, like Eon-Eok which can be zero.

So, one have to revised scheme to allow for degeneracy.

Suppose the S.E. for the perturbed system is;

( H o + H ′) | ψ p 〉 = E p | ψ p 〉

And the solution is;

| ψ p 〉 = ∑ c pj | j 〉
j

Substitute in S.E. and multiply by 〈 k |

∑ c pj 〈 k | H o | j〉 + ∑ c pj 〈 k | H ′ | j〉 = E p ∑ c pj 〈 k | j〉
j j j

∑c
j
pj
Eojδ kj + ∑ c pj ( H ′ )kj = E p ∑ c pjδ kj
j j

c pk Eok + ∑ c pj ( H ′) kj = E p c pk
j

c pk ( E p − Eok ) = ∑ c pj ( H ′ )kj ..........( ∗ )

j

For simplest, assume that we have only two degenerate eigen functions
| r 〉 and | s〉 where;
Eor = Eos

The effect of the perturbation is to mix the two eigen functions together.

| ψ p 〉 = ∑ c pj | j 〉
j

So, the perturbed wave functions |ψ r 〉 and |ψ s 〉 are;

| ψ r 〉 = crr | r 〉 + crs | s〉

| ψ s 〉 = c sr | r 〉 + c ss | s〉 , Er ≠ E s

Equation (*) can be written as;

c pk ( E p − Eok ) = c pr ( H ′ )kr + c ps ( H ′ )ks

Consider the perturbed state |ψ r 〉

c rk ( E r − Eok ) = c rr ( H ′) kr + crs ( H ′) ks

Which gives for;

k =r c rr {( H ′ )rr + E or − E r } + crs ( H ′ )rs = 0

k=s crr ( H ′ )sr + crs {( H ′ )ss + Eos − E r } = 0

These two equations have a solution if and only if there Wronksen is

zero; i.e.

( H ′ )rr + E or − E r ( H ′ )rs
=0
( H ′ )sr ( H ′ )ss + E os − E r

So, we can get;

Er2 − Er {( H ′ )rr + Eor + ( H ′ )ss + Eos } + {( H ′ )rr + Eor }{( H ′ )ss + Eos } −
( H ′ )rs ( H ′ )sr = 0
The solution of this quadratic equation is;

( H ′ )rr + ( H ′ )ss 1
Er = Eor +
2
{
m [( H ′ )rr − ( H ′ )ss ] 2 + 4 ( H ′ )rs
2
2
}
1
2

You should remember that Eor = Eos .

In the same procedure we can get Es .
Stark Effect of Hydrogen Atom (Sihff p252)

For n=2 energy level, there are 4 degenerate wave function;

| nlm〉 ⇒| 200〉 , | 210〉 , | 21 + 1〉 , | 21 − 1〉

Suppose that the electric field is applied in z- direction thus;

H ′ = eEz = eEr cosθ

The matrix of perturbation is;

〈 2l′m′ | eEr cosθ | 2lm〉 = eE ∫ψ 2*l′m′ r cosθψ 2lm dτ

Which consist of sixteen elements. By looking at the parity and the

symmetry, we can see that, the only non- zero elements;

( H ′) 210,200 = ( H ′) 200,210 = 〈 200 | eEr cosθ | 210〉

π 2π
eE ∞ 4
32πao4 ∫0
= r ( z − r / ao )e −r / a
dr .∫ sin θ .cosθdθ . ∫ dϕ
o

0 0

= −3eEao

Hence, the matrix of perturbation is;

 0 − 3eEao 0 0
− 3eEa 0 0 0
 o

 0 0 0 0
 
 0 0 0 0

Consider that;

| r 〉 =| 200〉 and | s 〉 =| 210〉 such that

Eor = Eos = E( n = 2 )

Thus; ( H ′ )rr = ( H ′ )ss = 0 and

( H ′ )rs = ( H ′ )sr = −3eEao

Therefore,

[
Er = E( n = 2 ) m ( H ′ )rs
2
]1
2

∴ Er = E( n = 2 ) + 3eEao

Es = E( n = 2 ) − 3eEao

\ψ r 〉
\ r〉 Er = E( n= 2 ) + 3eEao
4 − fold  2 − fold 
E( n = 2 )  
deg .states  deg .state 
\ s〉 E s = E( n =0 ) − 3eEao
\ψ s 〉

Before perturbation After perturbation

It can be easily seen that; crr / crs = 1. therefore;

H.W:
−1
|ψ r 〉 = 2 2 (ψ
200 +ψ 210 )
−1
|ψ s 〉 = 2 2 (ψ
200 −ψ 210 )

4∞ π 2π
eE  z  4 zr  − zr / a
.  ∫ r  2 − ao e o dr.∫ cos θ sin θdθ . ∫ dϕ
2
〈 200 | eEr cosθ | 210〉 =
16(2π )  ao  0 0 0

eE ∞ 4  r  −r / a π 2π
 
32πa o4 ∫0 
= . r 2 − e dr .∫ cos θ sin θ . ∫ dϕ
2 o

ao  0 0

∞ ∞

I = 2∫ r e 4 − r / ao
dr Γ ( x ) = ∫ e − t t x −1 dt
0 0

r
Let = t ⇒ r = ao t ⇒ dr = a o dt
ao
∞ ∞

∴ I = 2 ∫ a .t e .a o dt = 2 a ∫ t 4 e − t dt = ao5 Γ ( 5 ) = 2 a o5 .4 !
4
o
4 −t 5
o
0 0
 1 ∞ 5 −r / a
II = ∫ r e dr o

ao 0
1 ∞ 5 5 −t ∞

∫ o ∫
t 5 e − t dt = ao5 Γ ( 6 ) = ao5 5 !
5
= a o
t e a o
dt = a
ao 0 0

π
1
III = ∫ cos 2 θ sin θdθ = − (( −1 )3 − 13 ) = 2
0 3 3
∞

IIII = ∫ dϕ = 2π
0

∴ 〈 200 | eEr cosθ | 210〉 =

eE
32πao4
{ } 2
. 2a o5 .24 − ao5 .120 . .2π
3

eE 5 2
= ( 48 − 120 )a o
. .2π
32πa o4 3
eE 2
= .( −72 )a o5 . .2π
4
32πa o 3
eE 4
= .( −72) a o . = −3eEao
32 3
The Variation Method:

Occasions for use this method are;

1. When there is no similar problem capable of exact solution, so
perturbation theory can not used.
2. When there is a similar exact problem but perturbation term is too
large.
3. When the S.E. is non- separable and a large numerical solution
would be required.

The principle aim for using this method is; to calculate quickly an
upper bound for each of the two or three lowest energy level of the
system.

Energy Expectation Value:

Assume that the system have the following energy levels;

Eo 〈 E1 〈 E 2 〈 ....., with the corresponding eigen functions | 0〉, | 1〉,| 2〉,...., such
∧
as; H | n〉 = E n | n〉. According to the principle of linear superposition, any
arbitrary wave function ψ can be written in terms of the functions | n〉 as
follows;

| ψ 〉 = ∑ c n | n〉
n

Thus;
∧
∧ 〈ψ | H | ψ 〉
〈H〉 =
〈ψ | ψ 〉
But;
∧
〈ψ | H | ψ 〉 = ∑∑ cm cn E nδ mn = ∑ cn E n
* 2

n m n

〈ψ | ψ 〉 = ∑∑ cm cnδ mn = ∑ cn
* 2

n m n
 ∧
∴ 〈 H 〉 = ∑ c n E n / ∑ cn
2 2

n n

If we replaced each value En by Eo we get;

∑c
2
∧ n
〈 H 〉 ≥ Eo . n

∑c
2
n
n

∧
〈 H 〉 ≥ Eo
∧
〈ψ | H | ψ 〉
∴ Eo ≤
〈ψ | ψ 〉

Notes:

1. This provide an upper bound on Eo. Thus, it would be useful if the

right- hand side can be minimized.
2. In this method we choose a trial wave function with an adjustable
parameter and then we minimized the upper bound with respect to
this parameter.
3. The choice of the wave function is determined by the physics of
the system.

Minimization:

Choose the trial wave function ψ to be real for simplicity, and;

∧
∧
〈H 〉 ≡ ε =
∫ψ H ψdτ
∫ψ dτ
2

∧
ε ∫ψ 2 dτ = ∫ψ H ψ dτ

Vary ψ implicitly with respect to the adjustable parameter and find the
variation of ε as follows;

∧ ∧
(δε ) ∫ψ 2 dτ + 2ε ∫ψ .δψ dτ = ∫ (δψ H ψ + ψ H δψ )dτ
 ∧
Since H is Hermitical and ψ is real, thus;

∧ ∧
∫ψ H δψ dτ = ∫ δψ H ψ dτ
1  ∧
∴ δε  ∫ψ 2 dτ  = ∫ δψ ( H − ε )ψdτ
2 
The minimization condition is δε = 0

Case (i): if ψ is infinitely an adjustable, then δψ can take any value. Thus
we must have;
∧
H ψ = εψ

And hence;

ε = Eo And ψ =| 0〉
∧
Case (ii): when ψ is not infinitely an adjustable the minimization 〈 H 〉 is
used as an over estimate for Eo.
∧
h2 2
H =− ∇ +V
2m
h2
∧
− ∫ψ∇ 2ψdτ + ∫ψVψdτ
〈 H 〉 = 2m
∫ψ dτ
2

∫ψ∇ ψdτ = ∫ {∇.(ψ∇ψ ) − ( ∇ψ ).( ∇ψ )}dτ

2

= ∫ψ ( ∇ψ )ds − ∫ ( ∇ψ )2 dτ
s

= − ∫ ( ∇ψ )2 dτ

h2 2 2
∧ ∫ ∇ψ dτ + ∫ V ψ dτ
∴ 〈 H 〉 = 2m 2
∫ ψ dτ
 ∧
So, the minimization of 〈 H 〉 with respect to the parameter ( α ) i.e.
∧
∂〈 H 〉 / ∂α can be found from this equation.
Example: using the variatonal method find the energy and wave
function of ground state in the H- like atoms.

To choose the trial wave function we must note;

a) ψ must be spherically symmetrical.
b) ψ → 0 as r → ∞
c) ψ has no nodes.

Thus; suggest that

ψ = A exp( −αr / 2 )
1
∞
α3  2

A ∫e
2 − αr
4πr dr = 1 ⇒ A = 
2

0  8π 
∂ψ 1 1
− αr
∇ψ = = − αAe 2
∂r 2
∧  h 2 ∞ α 2 −αr ∞ −αr
e 
〈H 〉 = A2  ∫ ∫
2
e 4πr dr − Zk 4πr 2 dr 
 2m 0 4 0
r 

h 2α 2 Zkα
= −
8m 2
∧
∂〈 H 〉 h 2α Zk 2mZk
= − =0 ⇒α =
∂α 4m 2 h2

h 2 4m 2 Z 2 k 2 Zk 2mZk
∴ Emin = . − .
8m h4 2 h2

mZ 2 k 2 mZ 2 k 2
Emin = −
2h 2 h2
mZ 2 k 2
Emin = −
2h 2
3
Z  2 −1
ψ ground =  π 2 exp(− Zr / ao )
 ao 

Where k = e 2 / 4πε o and ao = 4πε o h 2 / me 2