Approximate Methods
Text: Ira N. Levine, Quantum Chemistry
• The Variation Method (Ch. 8)
• The Perturbation Theory (Ch. 9)
The Variation Method
o Approximates the ground-state energy of a system without
solving Schrodinger Equation.
o Based on the Variation Theorem
Variation Theorem (VT)
If φ is any well-behaved function of the coordinates of the system's
particles that satisfies the boundary conditions of the problem, then
* ˆ w: variation Integral
w H d
E φ : trial function
* 1 E1: Lowest energy
d H: Hamiltonian
The Variation Theorem allows to calculate an upper
bound for the system’s ground-state energy.
Variation Theorem
*Hˆ d
w E
* 1
d
Let the stationary-state eigenfunctions (exact wavefunctions) are ψk so that
Since ψk forms a complete, orthonormal sets of Ĥ, we can express as
Where,
Thus, (Proved)
Extension to Excited States
Consider extending the variation method to estimate the energy of
the first excited state.
Let the order of energies of stationary states be
For a normalized variational
function φ :
Further, restricting φ that are orthogonal to the true ground-state
wave function ψ1, so that
Thus,
Extension to higher excited states:
The restrictions (orthogonality) makes it troublesome to apply !
The Variation Method (summary)
* Approximates the ground state energy of a system without solving
Schrodinger Equation.
• Based on the Variation Theorem (VT) which states that if φ is any
well-behaved function of the coordinates of the system's particles
that satisfies the boundary conditions of the problem, then
*Hˆ d w: variation Integral
w
E φ : trial function
* d 1 E1: Lowest energy
H: Hamiltonian
• VT allows to calculate the upper bound for the system state
energy.
• Lower the value of w, the trial function will be closer to the actual
wavefunction ψ1.
• w approaches to E1 much faster than φ approaches to ψ1.
It is possible to get a rather good approximation to energy using
rather a poor trial function.
Linear variation functions
Parameterization of trail function (φ) by a linear combination of fixed
(linearly independent) basis functions (fi) with variable coefficients (ci)
The variational integral is
Where,
Linear variation functions, recap…
Parameterization of trail function (φ) by a linear combination of fixed
(linearly independent) basis functions (fi) with variable coefficients (ci)
The variational integral
The variational integral W is a function of the n independent variables
c1, c2,..., cn, and for a minimum in W ,
On simplification, this leads to a set of n simultaneous, linear, homogeneous
equations (called Secular Equation) in the n unknowns c1, c2,..., cn
Secular Equation
Linear variation functions, contd…
Secular Equation
Expansion of this determinant gives an algebraic equation of degree n in the
unknown W. This algebraic equation has n roots, which can be shown to be real,
let’s say
If the bound states energy of the system is in order
Then, it can be shown that
Thus, the linear variation method provides upper bounds to the energies of the
lowest n bound states of the system. The roots W1, W2,..., Wn are approximations
to the energies of the lowest states.
Linear variation functions, simplification
Secular Equation (8.56)
Secular Determinant
(8.59)
Linear variation functions, example
Find approximate energies and wave functions for the lowest four states of PID.
When the secular equation is in block-diagonal form, it factors into two or more
smaller secular equations, and the set of simultaneous equations breaks up into two
or more smaller sets of equations.
The Perturbation Theory
It is a systematic procedure for obtaining approximate solutions to the
perturbed problem, by building on the known exact solutions to the
unperturbed case.
Suppose we want to solve Perturbed system
(unknown)
However, we can solve
unperturbed system
Small perturbation (known)
How to relate the unknown eigenvalues and eigenfunctions of
the perturbed system to the known eigenvalues &
eigenfunctions of the unperturbed system?
(1) Time-independent (2) Time dependent
(A) non-degenerate
(B) degenerate
Time-independent, non-degenerate PT
The Schrodinger equation for the perturbed state
Now the Schrodinger equation:
Time-independent, non-degenerate PT
(First-order Perturbation Theory)
(Second-order Perturbation Theory)
First-Order Perturbation Theory
1st term LHS:
Second-Order Perturbation Theory
1st Order Corrections:
Sum is over different states rather than energy values.
Effect of perturbation is to “mix in” contributions from other states.
The Variation-Perturbation Method
The variation-perturbation method allows one to accurately
estimate E(2) and higher-order perturbation-theory energy
corrections for the ground state of a system without evaluating the
infinite sum in
The method is based on the inequality
where u is any well-behaved function that satisfies the boundary
conditions, and where the subscript g refers to the ground-state.
Perturbation Treatment for He ground state
Perturbation Treatment for He ground state
Variation Treatment for He ground state
Variation Treatment for He ground state
Variation Treatment for He ground state