Approximate methods
• Why we need approximate methods ?
Because Schrodinger equation for an atom or a molecule which contains
more than one electron cannot be solved exactly that means in principle
one can solve Schrodinger equation exactly only for hydrogen atom. So,
approximate methods are needed to solve Schrodinger equation for multi
electron systems.
• For multi electron systems, the major problem arise form the presence of
the inter-electronic repulsion terms and this term creates problems in the
solution therefore in order to solve Schrodinger equation for a chemical
system which is multi electron one uses approximate
• Mainly two types of approximate methods
(i) perturbation method (ii) variation method
Variation method
• Variation method is based on variation theorem.
• Theories of chemical bonding namely molecular orbital theory and
valence bond theory come from the application of variation theorem to
the electronic structure of molecules.
Variation theorem
• The variation theorem says that the expectation value of the energy for
any wave function is equal to or greater than the ground state energy.
• Suppose there is a quantum mechanical system for which Schrodinger
equation cannot be exactly solved. The corresponding Schrodinger
equation
Hˆ n = En n
(1)
• The exact wavefunction of this system for ground state is 0 , while
corresponding energy is E 0
• Suppose we guess the ground state wave function or what we call as trial
wave function or as a approximate wavefunction a
• Guessing is based on many physical and chemical considerations
a 0
• The corresponding energy Ea would be given by
* ˆ
Ea =
H a d
a
E0
a d
*
a
• This approximate energy according to variation theorem is always greater
than the exact energy E0. Ea will be equal to E0 only if the approximate
wave function is the ground state wave function.
• Also it is already assumed that Eq.1 (and similar) can not be solved exactly
therefore in this case approximate wave function will always give energy
greater than the corresponding exact energy and this is the definition of
the variation theorem.
Ea E0
• Closer the a is to 0 , the closer Ea will be to E0.
• Suppose we have two trial wavefunctions and each one of give the
approximate energies. Then that wave function which gives energy closer
to the exact energy will be the better wave function than the other.
Linear variation principle
• This principle helps us in constructing the approximate wave function
• According to linear variation principle, approximate wave function can be
written as a linear combination of the set of wavefunctions n
where, n ϵ 1, 2, 3 ………, which would have been obtained by the exact
solution of the Schrodinger equation.
• The trial wave function is expressed as a linear combination of a complete
set of normalized and orthogonal eigenfunctions
a = n an n
• an an are various coefficients.
Proof of Variation Theorem
• let's see how variation theorem can be proved through the use of this
linear variation principle
• if we take the approximate wave function then according to the variation
theorem the approximate energy Ea is given
Ea =
n
a Hˆ a d
n
*
n
*
n n n
(2)
a a d
*
n n n n n n
• assume n to be normalized
n n d = 1
*
n n n H n an n d n n n n H n d
* ˆ * ˆ
a *
a a *
Put it as denominator
Ea = =
an an *
nn
a a * in equation 2
Hˆ n = En n
n n
an an n En n d
* *
Ea = n
a a
n
n n
*
* 2
aa E a En
= =
n n n n n n
Ea
a a
n
n n
*
a n
2
n
subtracting E0 from both sides
an ( En − E0 )
2
E a − E0 = n
(3)
a
2
n
n
a 0 sum of +ve real numbers
2
En E0 As we defined E0 as the lowest energy &
n
n
E n − E0 0 This makes R.H.S of Eq.3 +ve, so L.H.S difference must give Ea greater
than E0
This is the statement of variation theorem. Whenever trial wavefunction
E a E0 is used then corresponding energy calculated using variation theorem
will be greater than the corresponding exact ground state energy
