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You are on page 1of 4

Recall the variational principle. See Chapter 7 of the textbook. The variational

theorem for a Hermitian operator H with the smallest eigenvalue E0 states that for any

normalized |ψi we have

E0 ≤ hψ|H|ψi .

Given a Hamiltonian the method consists in starting with a clever and tractable guess for

the so-called trial wave function with one (or more) free (variational) parameters. Nor-

malize the wave function and evaluate hψ|H|ψi. This yields a function of the variational

parameters. Find the value of the parameters that minimizes this function and this is the

variational estimate for the ground state energy.

In Helium we place the two electrons in a 1s-like state with the spatial part being

symmetric (both electrons are in the same state) and the spin part in the antisymmetric

spin singlet. So we write the spatial part of the wave function as

φ(~r1 ) φ(~r2 )

where we will determine the functional form of φ0 using the variational approach1 . We

try a form inspired by the 1s state of the hydrogen atom which is exponentially decaying:

1

φ(r) = √ 2α3/2 e−αr .

4π

This is normalized and has one variational parameter α which controls the spatial extent

of the wave function. The angular part is a constant, i.e., ` = 0. The Hamiltonian is

given by

h̄2 2 h̄2 2 Zq 2 Zq 2 q2

H = − ∇1 − ∇2 − − +

2m 2m |~r1 | |~r2 | |~r1 − ~r2 |

where the first two terms correspond to the kinetic energies of the two electrons and the

last term is the Coulombic repulsion between the two electrons. For Helium the nuclear

charge Z = 2. We need to evaluate hΨ|H|Ψi. The first term we need is

Z Z Ã !

3 3 ∗ ∗ h̄2 2

d r1 d r2 φ (~r1 ) φ (~r2 ) − ∇ φ(~r1 ) φ(~r2 ) .

2m 1

Since the operator only involves the first coordinate ~r1 the integral over d3 r2 yields 1 since

φ(~r2 ) is normalized. We are left with

Z Ã !

3 h̄2 2

d r1 − ∇ φ(~r1 )

2m 1

1

Note that the actual wave function will not be of this form and can depend upon |~r1 − ~r2 | which

cannot be written as a product of a function of ~r1 and ~r2 separately. However, we choose the product

form for calculational convenience. If we want a better approximation to the ground state energy we can

use other forms of the wave function.

1

and this is the same calculation as the kinetic energy of the electron in the hydrogen atom

h̄2 α2

and we find 2m

; this must be multiplied by a factor of 2 for the kinetic energy of the

second electron which involves identical integrals.2 Now for the potential energies. For

the attractive energy of the first electron and the nucleus we have

Z Z Ã !

3 3 ∗ ∗ Zq 2

d r1 d r2 φ (~r1 ) φ (~r2 ) − φ(~r1 ) φ(~r2 ) .

r1

Z Ã !

3 ∗ Zq 2

d r1 φ (~r1 ) − φ(~r1 )

r1

which can be done since this is spherically symmetric and yields −αZq 2 ; this should

also be multiplied by 2 for the contribution from the other electron.

The interaction energy is much harder to calculate (Please see the next page if you

are mathematically curious) and yields 5q 2 α/8. Together we have

µ ¶

h̄2 α2 5

E(α) = − q 2 α 2Z − .

m 8

Minimizing with respect to α we obtain3

µ ¶

mq 2 5

α∗ = Z− .

h̄2 16

The minimum energy is given by E(α = α∗ ) and is

µ ¶2

mq 4 5

Eg = − 2 Z− .

h̄ 16

Recall that the ground state of the hydrogen atom is given by

mq 4

E0 = − .

2h̄2

Thus we write our estimate of the ground state energy is

µ ¶2

5

Eg = −2E0 Z− .

16

2

Observe that when the Hamiltonian involves a single-particle term, i.e., depends on the coordinates of

one of the particles only, the expectation value involves a three-dimensional integral over the coordinates

of that particle only. Which of the terms in the Hamiltonian is not single-particle?

3

µ ¶¯

2h̄2 α 2 5 ¯¯

− q 2Z − = 0

m 8 ¯α=α∗

2

If we had just naively used the 1s hydrogen atom energy except with nuclear charge Z,

each electron would have an energy −E0 × Z 2 and so for two electrons we would have

−2E0 Z 2 . Instead the nuclear charge is reduced from Z = 2 to a lower value thanks to

the shielding effect of the other electron.

What is measured is not the ground state energy but the ionization energy. This is

the energy required to remove the most weakly bound electron from the atom. It is given

by the difference Eion − Eatom .

First the energy of the helium ion. A singly ionized Helium atom looks like a hydrogen

atom with a nuclear charge 2. The latter has an energy −4E0 .

We have computed the energy of the atom Thus the ionization energy is 2E0 (2−(5/16))2 −

4E0 = E0 (217/128 which yields 23.05eV compared to the observed value of 24.59eV .

S. Chandrasekhar and G, Herzberg used 10 variational parameters and later 18. Later T.

Kinoshita used 39 and later 80 parameters.

Calculation of the interaction energy for the Helium atom with the simplest

variational ansatz

The trial wave function is given by

1

u(~r) = √ 2α3/2 e−αr .

4π

We need to evaluate the six-dimensional inetgral

Z Z

3 q2

I ≡ d r1 d3 r2 |u(~r1 )|2 |u(~r2 )|2 .

|~r1 − ~r2 |

There are many ways of doing this integral. Here is one: We use the fact that the

(three-dimensional) Fourier transform of the Coulomb potential is 4π/k 2 , a very important

result4 : Z

1 d3 k 4π i~k·(~r1 −~r2 )

= e .

|~r1 − ~r2 | (2π)3 k 2

Substituting this in the integral and changing the orders of integration

Z

d3 k 4πq 2 Z 3 2 i~k·~

r1

Z

~

I = 3 2

d r1 |u(~r1 )| e d3 r2 |u(~r2 )|2 e−ik·~r2 .

(2π) k

Clearly, we need we need the Fourier transform of |u(~r)|2 which occurs twice:5

Z

~ α3 −2αr1

d3 r1 eik·~r1 e .

π

4

One way of convincing yourself of this is to Fourier transform the equation

µ ¶

1

∇2 = −4πδ(~r) .

r

5

Since we can change ~r2 → −~r2 the sign of the argument in the exponential does not matter.

3

Z Z π Z 2π

~ ~ sin(kr1 )

Using dΩ eik·~r1 ≡ dθ sin θ dφ eik·~r1 = 4π

0 0 kr1

we have

Z Z ∞

~ α3 −2αr1 sin(kr1 ) −2αr1 16α4

d3 r1 eik·~r1 e = dr r2 4α3 e = .

π 0 kr1 (4α2 + k 2 )2

Z Ã !2

d3 k 4πq 2 16α4 5 2

= q α.

(2π)3 k 2 (4α2 + k 2 )2 8

6

The angular part of this integral is 4π since the integrand is independent of angles and so we need

an integral over k only that can be done using Mathematica if you wish.

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