Variational Method Online Lecture-Notes

6/4/2024
1 Quantum Mechanics-II
By
Dr. Muhammad Nasir Rasul
Assistant Professor
Department of Physics,
The Islamia University of Bahawalpur
2 Lecture # 6
Variational Method
3 Need of Variational Method
• What should we do when the system under consideration do not match with any of
the exact system that can be solved exactly or we have solved that exactly.
• When even the Hamiltonian is known but cannot be solved exactly or even
approximately using other methods e.g. perturbation method.
• Then the method for solving that kind of problems is the variational method.
• This is also called “Rayleigh-Ritz method”.
• Variational method do not require the knowledge of simple Hamiltonian to solve the
problem.
• This method is useful for determining the upper bound values for energy
eigenstates of a system whose Hamiltonian is known whereas its eigenstates &
eigenvectors are not know.
4 Variational Method
• The variational method does not use the eigenvalue problem to solve the system
i.e. 𝑯|𝝋⟩ = 𝑬|𝝋⟩
• It uses a variational scheme to find the approximate eigenstates and Eigen energies
via variational equation;
𝜹𝑬(𝝍) = 𝟎 (1
Where "𝐸(𝜓)” is the expectation value of the energy of the state "|𝜑⟩";
𝝍𝑯𝝍
𝑬 𝝍 = (2
𝝍𝝍
• Now we suppose that the state “|𝝋⟩” depends on any parameter “α” then “E” will
also ultimately depend on “α”.
• The variational equation (1) will allow to change the value of “α” so as to minimize
"𝑬(𝝍)” .
• The minimum value of "𝑬(𝝍)” then provide an upper limit approximation for the
true ground state energy of the system.
5 Statement
• The approximate minimum energy “𝑬𝒎𝒊𝒏 ” of a system calculated through a trial
wavefunction is always an upper bound of true ground state energy "𝑬𝒐 “.
OR
• The best value of any variable parameter “α” in an approximated wavefunction is
that which minimizes the energy of the ground state.
• Mathematically;
𝝍𝑯𝝍
𝑬𝒎𝒊𝒏 𝝍 = ≥ 𝑬𝒐
𝝍𝝍
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6/4/2024
𝝍𝑯𝝍
𝑬𝒎𝒊𝒏 𝝍 = ≥ 𝑬𝒐 (3
𝝍𝝍
• The equality condition in above expression occurs only when the trial wavefunction
"|𝝍⟩" become very close or equal to true ground state wavefunction " 𝝍𝒐 “.
6 Proof
• Let consider a quantum system which is described by a Hamiltonian with a series of
eigenstates with corresponding eigenvalues i.e. 𝑯 𝝍𝒊 = 𝑬𝒊 𝝍𝒊
• We want to solve the eigenvalue equation for this system for ground state, but we
are not able to solve it.
• Thus we adopt the procedure of “variational method” given in equation (3) i.e.
𝝍𝑯𝝍
𝑬𝒎𝒊𝒏 𝝍 = ≥ 𝑬𝒐
𝝍𝝍
• As the unknown wavefunction (trial wavefunction) form a complete set, we can
express our wavefunction as a linear combination;
𝝍𝒕𝒓𝒊𝒂𝒍 = 𝒄𝒏 𝝍 𝒏
𝑛
From equation (3) we need 𝝍 𝝍 so;
𝝍𝝍 = 𝒄𝒎 𝝍 𝒎 𝒄𝒏 𝝍 𝒏
𝑚 𝑛
𝝍𝝍 = 𝒄∗𝒎 𝒄𝒏 𝝍𝒎 𝝍𝒏
𝒎 𝒏
𝝍𝝍 = 𝒄∗𝒎 𝒄𝒏 𝜹𝒎𝒏 = 𝒄𝒏 𝟐
𝒎 𝒏 𝒏
7 Proof
From equation (3) now we need 𝝍 𝑯 𝝍 so;
𝝍𝑯𝝍 = 𝒄𝒎 𝝍 𝒎 𝑯 𝒄𝒏 𝝍 𝒏
𝑚 𝑛
𝝍𝑯𝝍 = 𝒄𝒎 𝝍𝒎 𝑬𝒏 𝒄𝒏 𝝍 𝒏
𝑚 𝑛
𝝍𝑯𝝍 = 𝒄∗𝒎 𝒄𝒏 𝑬𝒏 𝝍𝒎 𝝍𝒏
𝒎 𝒏
𝝍𝑯𝝍 = 𝒄∗𝒎 𝒄𝒏 𝜹𝒎𝒏 = 𝑬𝒏 𝒄𝒏 𝟐
𝒎 𝒏 𝒏
8 Proof
Putting the value of 𝝍 𝝍 and 𝝍 𝑯 𝝍 in equation (3) we get;
𝝍𝑯𝝍
≥ 𝑬𝒐 (3)
𝝍𝝍
∑𝒏 𝑬𝒏 𝒄𝒏 𝟐
∑𝒏 𝒄𝒏 𝟐
≥ 𝑬𝒐
𝑬𝒏 ∑𝒏 𝒄𝒏 𝟐
≥ 𝑬𝒐
∑ 𝒏 𝒄𝒏 𝟐
𝑬𝒏 ≥ 𝑬𝒐
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6/4/2024
≥𝑬
𝒏 𝒄𝒏
𝑬𝒏 ≥ 𝑬𝒐
Hence this proves the statement of variational method mathematically.
9 Procedure to apply variational method

• By following the steps given below we may apply the variational method to find the
minimum ground state energy of quantum system;
1) Make an educated guess of trial wavefunction taking into account all the physical
properties i.e.
• Symmetry
• Boundary conditions
• Smoothness
• Behavior at infinity
Add some adjustable parameters i.e. α1 , α2 , α3 , ……. Which will account for the
properties that may not be guessed as;
𝝍𝒕𝒓𝒊𝒂𝒍 = 𝝍𝒕𝒓𝒊𝒂𝒍(α1 , α2 , α3 , …….)
10 Procedure to apply variational method

2) Calculate energy by using the relation below;
𝝍 (α1 , α2 , α3 , …….) 𝑯 𝝍𝒕𝒓𝒊𝒂𝒍(α1 , α2 , α3 , …….)
𝑬𝒏 α1 , α2 , α3 , ……. = 𝒕𝒓𝒊𝒂𝒍
𝝍𝒕𝒓𝒊𝒂𝒍(α1 , α2 , α3 , …….) 𝝍𝒕𝒓𝒊𝒂𝒍(α1 , α2 , α3 , …….)
3) Calculate for minimum “𝑬𝒎𝒊𝒏 ” by using variational equation i.e. by varying
adjustable parameters “α𝑖 ” as;
𝝏 𝝍 (α𝑖 ) 𝑯 𝝍𝒕𝒓𝒊𝒂𝒍 (α𝑖 )
𝑬 (α ) = 𝒕𝒓𝒊𝒂𝒍
𝝏α𝑖 𝒏 𝑖 𝝍𝒕𝒓𝒊𝒂𝒍 (α𝑖 ) 𝝍𝒕𝒓𝒊𝒂𝒍 (α𝑖 )
From this solution we will get those values of "α𝑖 ” which minimized “𝑬𝒏 ” to “𝑬𝒎𝒊𝒏 ” .
4) Substitute these"α𝑖 ” values to equation at the top of this slide to get minimum
eigenenergy and corresponding eigenstate.

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6/4/2024

𝝍𝑯𝝍 = 𝒄∗𝒎 𝒄𝒏 𝜹𝒎𝒏 = 𝑬𝒏 𝒄𝒏 𝟐

9 Procedure to apply variational method

10 Procedure to apply variational method

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