Variational Principle

Formula:
⟨ φ|^
H |φ ⟩
H ⟩=
⟨^
⟨ φ|φ ⟩ ; where φ is the trial wave function.
and variational principle also states that E1 ≤ ⟨ ^
H⟩

−ℏ 2 ∂2
^
H= +v( x) , i.e., Hamiltonian operator.
2 m ∂ x2

In order to get minimum energy, find the value of α from the equation
ⅆ ⟨^
H⟩
=0, where α is the variational parameter and put it into the
ⅆa
H ⟩.
expression of ⟨ ^

Problem:
1. Optimize the trial function exp(-αr) and evaluate the
ground state energy of the hydrogen atom.
^ −ℏ 2 2 ⅇ2
Ans: H= ∇− ; in spherical polar coordinate
2m 4 π ϵ0 r
1 ∂ 2 ∂
∇ 2=
r2 ∂ r
r
∂r( ) when ψ is only function of r.
2
1 ∂ 2 ∂
⟨ T^ ⟩= −ℏ ∫ exp (−αr ) 2
r ( ) 2
exp (−αr ) 4 π r dr
2m r ∂r ∂r

−ℏ2 ∂2
¿
2m
4π ∫ r exp (−αr ) ∂ r 2 exp (−αr ) dr +∫ r 2 exp (−αr ) 2r ∂r∂ exp (−αr ) dr
[ 2
]
∞ ∞
−ℏ2
¿
2m 0
[
4 π α 2∫ r 2 exp (−2 αr ) dr−2 α ∫ r exp (−2 αr ) dr
0
]
 −ℏ2 2 π 4π ℏ2 π
¿
2m [ ( ) ( )]
α ¿ 3 −2 α∗
α 4 α2
=
2mα
∞
ⅇ2 ⅇ2
o ⟨ V ⟩=∫
0 4 π ϵ0 r
exp (−2 αr ) 4 π r 2 dr=
4 ϵ0 α2

o ⟨ φ|φ ⟩=4 π ∫ r exp (−2 αr ) dr= απ

2
3
0

ℏ2 α 2 ⅇ2 α
o ⟨ H ⟩= −
2 m 4 ϵ0 π

ⅆ ⟨^
H⟩ mⅇ 2
o now, ⅆα
=0 ; α =
4 πϵ 0 ℏ2
=1/a0 ; a 0 is the Bohr Radius

−m ⅇ 4
o Emin = ⟨ H ⟩min =
32 π 2 ϵ 20 ℏ2

1
1 −r
o trial wavefunction φ=
π a03 ( ) 2
exp(
a0
)