Approximation method

• The Schrodinger equation does not directly solve many-electron systems like the He
atom.
• Even the perturbation theory cannot be used for solving such a system. Hence, the
need for an approximation method.
• If  is the trial wave function of a system, then energy E calculated based on the trial
wave function will always E  E0. (true/lowest E of the system)
Variation method:
Let us guess the approximation wave function . The expectation energy is given by
∫ ∗ ̂
𝐻  
⟨𝐸⟩ =
∫ ∗  

 is normalized denomination ∫ ∗   = 1
⟨𝐸⟩ = ∫ ∗ 𝐻
̂  

The bracket notation is

⟨𝐸⟩ = ⟨∗ |𝐻
̂ | ⟩ ……1
̂ - complete Hamiltonian of the system.
𝐻

It can be proved thus the energy E is always greater than the true energy E0 of the system
of its ground states (or) greater than the lowest eigenvalues of the system.
We can make several guesses of wave functions 1 and 2 which lead to energy E1 and E2,
respectively. Then in accordance with the variation principle, if E1  E2, E1 is a better
approximation than E2 to the true energy E0. So 1 will be a better wave function of the
system than 2.

Variation theorem:

⟨∗ |𝐻
̂ | ⟩ = E  E0
̂ .  is
E0 is the true energy of the system in the ground state (or) the lowest eigenvalue of 𝐻
normalized eigen function. In other words, the calculated energy E is always greater than E0.
This is the variation theorem.
Proof:
Let us choose a set of wave functions. The 𝜙0 , 𝜙1 , 𝜙2 , etc., which are individually
normalized and mutually orthogonal. This is an orthonormal set. They are also the
̂ with eigen values E0, E1, E2, etc. The general wave function is,
eigenfunction of 𝐻
 ̂ 𝜙𝑖 = Ei 𝜙𝑖
𝐻 ……2
Where i = 0,1,2...
According to the expansion theorem,
 = ∑𝑖 𝑐𝑖 𝜙𝑖 ……3
∗ = ∑𝑖 𝐶𝑖∗ ⋅ 𝜙𝑖∗

 ∫ ∗  ⅆ = ∫ ∑𝑖 𝐶𝑖∗ ⋅ 𝜙𝑖∗ ∑𝑖 𝑐𝑖 𝜙𝑖 

= ∑𝑖 𝐶𝑖∗ 𝑐𝑖 ∫ 𝜙𝑖∗ 𝜙𝑖 

= ∑𝑖 |𝐶𝑖 |2 × 1

∑𝑖 |𝐶𝑖 |2 = 1

Inserting the equation 3 into the equation 1

E = ⟨𝐸⟩ = ∗ ⟨𝐻
̂ ⟩  …….1

̂ ∑𝑖 𝑐𝑖 𝜙𝑖 ⅆ
E = ∫ ∑𝑖 𝐶𝑖∗ ⋅ 𝜙𝑖∗ 𝐻 ⸪ ̂ (c1 1+ c2 2+……) 
∫ ( 𝑐1∗ 𝜙1 * + 𝑐2∗ 𝜙2 *+…) 𝐻

̂ 𝜙1 ⅆ  + 𝑐2∗ c2∫ 𝜙2∗ 𝐻

= 𝑐1∗ c1∫ 𝜙1∗ 𝐻 ̂ 𝜙2 ⅆ ……

̂ 𝜙𝑖 ⅆ 
= ∑𝑖 𝐶𝑖∗ 𝑐𝑖 ∫ 𝜙𝑖∗ 𝐻

= ∑𝑖 |𝐶𝑖 |2 ∫ 𝜙𝑖∗ 𝜙𝑖 Ei ⅆ

= ∑𝑖 |𝐶𝑖 |2 Ei ∫ 𝜙𝑖∗ 𝜙𝑖 ⅆ 

E = ∑𝑖 |𝐶𝑖 |2 Ei  1

̂.
If E0 is the lowest eigenvalue of 𝐻
Then E – E0 = ∑𝑖 |𝐶𝑖 |2 Ei – E0

= ∑𝑖 |𝐶𝑖 |2 Ei - ∑𝑖|𝐶𝑖 |2 E0

 E-E0 = ∑𝑖 |𝐶𝑖 |2 (Ei – E0) …….4

The quantity Ei – E0 must be positive or zero for all values of i.

Since, |𝐶𝑖 |2 is always positive.

 RHS of equation 4 is always positive or zero.

(Ei – E0) ≥0 or
E ≥ E0.
Application of variation theorem to He – atom:

=r12

-e -e
r1 r2

+2e
2ⅇ2 2ⅇ2 ⅇ2
V=- - +r
r1 r2 12

2 2 1
=- -r +r
r1 2 12

ℏ2 ℏ2 2ⅇ2 2ⅇ2 ⅇ2
̂=-
𝐻 𝛻12 - 𝛻22 - - +r
2𝑚1 2𝑚2 r1 r2 12

1 1 2 2 1
= - 2 𝛻12 - 2 𝛻22 - -r +r
r1 2 12

[In a.u ℏ=1, m1=m2=1, e=1]

A slater determinant will give the overall wave function of the He atom.
1
𝛹0 = |1𝑠(1). 1𝑠(2)|
√2
1𝑠(1) stands for the spin-orbital in He atom
1𝑠(2) indicate it’s antisymmetric.
On expansion
1
𝛹0 = 1𝑠(1). 1𝑠(2)[𝛼(1)𝛽(2) − 𝛼(2)𝛽(1)]
√2
Hence, Slater determinant
1𝑠(1)𝛼(1) 1𝑠(1)𝛽(1)
𝛹0 = N | |
1𝑠(2)𝛼(2) 1𝑠(2)𝛽(2)
= N [1s(1) 𝛼(1). 1𝑠(2)𝛽(2) - 1𝑠(1)𝛽(1). 1𝑠(2)𝛼(2)]
= N {1s(1). 1𝑠(2)[𝛼(1). 𝛽(2) - 𝛼(2). 𝛽(1) ]}
We know that there is no difference between the spin states. Each electron has =1/2.
We can represent the spin wave function for these two states by & corresponding = +1/2,
= -1/2.
S = space part; & = spin part.
The combined space & spin function of an electron is called the spin-orbital wave function of
many-electron systems and can be solved by using the slater determinant.
 ̂ |𝜓〉
E = 〈𝜓|𝐻 [hence E= 𝛹0 𝛹0 = 02]

The determinantal form of the wave function of a many electrons system is referred to
as the slater determinant. The elements of the determinant are abbreviated further by using the
fact that each orbital in an atom or molecule can accommodate two electrons, one with  spin
& other with  spin.
1
E ={ 1s(1). 1𝑠(2)[ 𝛼(1). 𝛽(2) - 𝛼(2). 𝛽(1)]}2
√2
1
E = 2 1s(1). 1𝑠(2) |𝐻
̂ |1s(1). 1𝑠(2)   𝛼(1). 𝛽(2) - 𝛽(1) 𝛼(2)  𝛼(1).

𝛽(2) - 𝛽(1) 𝛼(2)  ………1

Solving the second part of eqn 1 by integral

 𝛼(1). 𝛽(2) - 𝛽(1) 𝛼(2)  𝛼(1). 𝛽(2) - 𝛽(1) 𝛼(2) 

= 2(1)ds1 2(2)ds2 + 2(2)ds2 2(1)ds1 - 2(1)(2) ds1 (2)(1) ds2

Part is orthogonal so it is zero.

= 11 + 11 – 0 = 1+1=2

1
E= 2 1s(1). 1𝑠(2) |𝐻
̂ |1s(1). 1𝑠(2)   2

̂ |1s(1). 1𝑠(2) 
E=1s(1). 1𝑠(2) |𝐻

Now we can write the Hamiltonian

̂ = H1+H2+ 1
𝐻 r 12

1 2
Where H1 = - 𝛻2 -r
2 1 1

1 2
H2 = - 𝛻2 -r
2 2 2

1 2
In general, Hi = - 𝛻2 - r
2 𝑖 i

Total energy E = 1s(1). 1𝑠(2) |𝐻

̂ |1s(1). 1𝑠(2) 
1
= 1s(1). 1𝑠(2) |𝐻1 + 𝐻2 + |1s(1). 1𝑠(2) 
r12

= 1s(1). 1𝑠(2) |𝐻1 |1s(1). 1𝑠(2)  + 1s(1). 1𝑠(2) |𝐻2 |1s(1). 1𝑠(2)  +1s(1).
1
1𝑠(2) |r |1s(1). 1𝑠(2) 
12

= 1s(1) |𝐻1 |1s(1)  1𝑠(2)  1𝑠(2)  + 1s(2) |𝐻2 |1s(2)  1𝑠(1)  1𝑠(1)  +1s(1).
1
1𝑠(2) | |1s(1). 1𝑠(2) 
r12
 1
= 1s(1) |𝐻1 |1s(1)  + 1s(2) |𝐻2 |1s(2)  + 1s(1). 1𝑠(2) |r |1s(1). 1𝑠(2) 
12

 E= E1S(1) +E1S(2)+J …….2

J is coloumbic repulsion between electrons (i.e.) interaction term between electron 1
&electron 2.
E1s(1) is the energy of electron 1 in the 1s orbital of the He atom,
E1s(2) is the energy of electron 2 in the 1s orbital of the He atom.
Part I
If electron 1 when it is away from the nucleus, the potential is
He (++) nucleus
2nd e- 1st e-
−𝑒 ×(2−1)𝑒
= r

−(2−1) 2 1
= e =−r
r

When the electron 1 comes very close to the nucleus, the electron goes far away from the
nucleus.
He (++) nucleus
1st e- 2nd e-

−𝑒×2𝑒 2 2
= = - r e2 = - r a.u
r

When the electron is in between the two extremes, the effective nuclear charge experienced
by the electron is Z’. It has a value between 1 and 2. The best value of Z’ is found out by the
variation principle.
Part II:
The wave function of 1s orbital corresponding to the effective nuclear charge Z’ is
given by
1
3 2
𝑧′ ′𝑟
1s = ( 𝜋 ) 𝑒 −𝑧

̂.
The orbital wave function is eigen function of 𝐻
′2
̂ = - 1 𝛻 2 - 𝑧′ with eigenvalue = 𝑧
Where 𝐻 2 r 2

Now E1s(i) = 1s(i) |𝐻

̂ |1s(i) 
1 2
= 1s(i) |− 𝛻𝑖2 − 𝑟 |1s(i) 
2 𝑖
We can write
2 −𝑧 ′ −(2−𝑧′) 𝑧′ 2 𝑧′
-𝑟 = - -𝑟 +𝑟
𝑖 𝑟𝑖 𝑟𝑖 𝑖 𝑖

−𝑧′ (2−𝑧′)
= -
𝑟𝑖 𝑟𝑖

1 𝑧′ (2−𝑧 ′ )
E1s(i) = 1s(i) |− 𝛻𝑖2 − 𝑟 − |1s(i) 
2 𝑖 𝑟𝑖

1 𝑧′ (2−𝑧 ′ )
= 1s(i) |− 𝛻𝑖2 − 𝑟 |1s(i)  - 1s(i) | |1s(i) 
2 𝑖 𝑟𝑖
2
𝑧′ 1
=-  1s(i)  1s(i)  – (2-z’) 1s(i) |𝑟 |1s(i) 
2 𝑖

𝑧 ′2 1
=- - (2-z’) 1s(i) |𝑟 |1s(i) 
2 𝑖

Since the electron 1 & 2 are equal. So the E1s(1) & E1s(2) are equivalent.
The total energy,
E= E1s(1) + E1s(2)+J
= 2 E1s(i)+J
1
= -z’2 – 2(2-z’) 1s(i) | |1s(i)  +J
𝑟𝑖

Evaluation of integral,
∞
1 1
1s(i) |𝑟 |1s(i)  = ∫ 1s(i) × 𝑟 × 1s(i) 𝜕𝜏
𝑖 1
0
∞ 1 1
3 2 3 2
𝑧′ −𝑧 ′ 𝑟 1 𝑧′ ′
=∫ (𝜋) 𝑒  𝑟  ( 𝜋 ) 𝑒 −𝑧 𝑟 𝜕𝜏
1
0
∞ ′ 3 −2𝑧′𝑟
𝑧 𝑒 1
=∫ 𝜕𝜏 =r2dr.sin d d
𝜋 𝑟1
0
3 ∞ −2𝑧′𝑟
𝑧′ 𝑒 1 𝜋 2𝜋
= ∫ r12 dr1 ∫0 sin 𝜃 𝜕𝜃 ∫0 𝜕𝜙
𝜋 𝑟1
0

𝑧 ′3 ∞ ′
= ∫ 𝑒 −2𝑧 𝑟 . r1 dr1.2.2
𝜋 0
∞ ′ 𝜋
= 4z’3 ∫ 𝑒 −2𝑧 𝑟 . r1 dr1 ∫0 sin 𝜃 𝜕𝜃= - (cos)0
0

= -(-1-1)=2
2𝜋
∫0 𝜕𝜙 = 2
 ’3 1!
= 4z
[2𝑧 ′ ]1+1

3
4𝑧 ′
= 2 = z’
4𝑧 ′

1
1s(1) |𝑟 |1s(1)  =z’
𝑖

The value of J has been calculated as 5/8 z’

 Total energy
E= -z’2 – 2 (2-z’)z’+ 5/8 z’
= - z’2 – 4z’+2z’2+5/8 z’
= z’2 – 4z’+5/8 z’
32 𝑧 ′ −5𝑧′
= z’2 -[ ]
8
27
= z’2 – z’
8

According to the variation method, the energy (E) is differentiated with respect to z’ & the
obtained value is zero. (z=0)
27
E= z’2 – z’
8

𝜕𝐸 27
= 2z’- 8 = 0
𝜕𝑧 ′
27
2z’= = 1.69
8

Then the energy becomes

27
E= (1.69)2 -  1.69
8

= -2.8476 a.u
= -77.48 eV
The experimental value is
E= -2.904 a.u
= -79.00 eV
The accuracy is 98%. This simple calculation accounts for 98% of the observed energy to an
electron. The effective nuclear charge of 1.69 instead of the true charge of 2. The quantity 0.31
represents the screening of the nuclear by the other electrons.