Lecture 21.

The Variational Method

* Degenerate perturbation theory

 The coupled quantum well

* The Variational method

 The triangular well

 Degenerate Perturbation Theory

• Here we discuss the application of DEGENERATE perturbation theory to the problem of

COUPLED quantum wells

* The system we consider is shown below and consists of a well centered on xL and
another that is centered on xR

 This problem CAN be solved exactly using a discussion of T-matrices

* It seems a reasonable GUESS however that the lowest two states of the double well
should consist of a MIXTURE of the lowest states (L & R) in each of the two wells

 We therefore develop a treatment of DEGENERATE perturbation theory in terms

of these two states

• THE PROBLEM OF COUPLED QUANTUM WELLS THAT WE

STUDY HERE IS ANALOGOUS TO THAT OF A DIATOMIC
MOLECULE

• THE COUPLING STRENGTH BETWEEN THE TWO WELLS

IS DETERMINED BY THE STRENGTH OF THEIR COMMON
BARRIER

• THE GROUND-STATE WAVEFUNCTIONS OF THE TWO

WELLS ARE ALSO SHOWN
 Degenerate Perturbation Theory

• We begin by writing the Schrödinger equations for the left and right wells INDIVIDUALLY
as
(T  VL ) L   L (21.1) (T  VR ) R   R (21.2)

* The next step is to write the wavefunction for the COUPLED system as a linear sum of
single-well eigenfunctions

   an n (21.3)
n

* With this definition the Schrödinger equation for the coupled system becomes

H n
mn an  E  S mn an
n
(21.4)

 Where we have defined the following matrix elements as

*
H mn    H n ( 21.5) S mn    m*  n (21.6)
m
 Degenerate Perturbation Theory

• While we are used to matrix elements of the form of Smn VANISHING when m  n due to
the property of orthonormality this is NOT the cases here

S mn    m*  n   mn ( 21.7)

* The point here is that the wavefunctions L and R are instead solutions to SEPARATE
Schrödinger equations

* The matrix equation to be solved is now a generalized eigenvalue problem

H a  ES a (21.8)

L(x)  R(x)
L R
• THE EIGENFUNCTIONS L AND R ARE NOT ORTHONORMAL
SINCE THEY ARE SOLUTIONS TO SEPARATE SCHRÖDINGER
EQUATIONS

• THE POINT TO NOTE IS THAT THE TWO WELLS ARE SHIFTED

FROM EACH OTHER BY A DISTANCE xR – xL

• IF WE CONSIDER ANY GIVEN EIGENSTATE OF THE INDIVIDUAL

WELLS THEN WE CANNOT SAY THAT L(x) = R(x)
 Degenerate Perturbation Theory

• The Hamiltonian may be solved here may be written in the form

H H LR 
H   LL ( 21.9)
 H RL H RR 

* We begin by calculating the matrix element HLL which may be written as

H LL    L* (T  VL  VR ) L      L*VR L    c (21.10)

 The additional term –c here is referred to as the CRYSTAL FIELD and gives the
expectation value of the added potential VR for the wavefunction L and we
denote this term as –c to remind us that the potential wells are ATTRACTIVE

 The other DIAGONAL element is of the same form as Eq. 21.10

H RR    R* (T  VL  VR ) R      R*VL R    c (21.11)
 Degenerate Perturbation Theory

• Similarly it can be shown that the two OFF-DIAGONAL terms are also EQUAL

H RL    R* (T  VL  VR ) L     R* L    R*VR L  s  t  H LR (21.12)

* The integral t is referred to as the TRANSFER, TUNNELING or OVERLAP INTEGRAL

* The integral s results from the NON-ORTHOGONALITY of the basis functions L and R
and from its definition the matrix S that appears in Eq. 21.8 may be written as

1 s 
S  (21.13)
 s 1

 With these results the matrix form of the Schrödinger equation may be written as

   c s  t  1 s 
s  t   c  a  E  s 1 a (21.14)
   
 Degenerate Perturbation Theory

• Solution of Eq. 21.14 requires

E   c Es  s  t
det( E S H)  0  det 0 (21.15)
Es  s  t E   c

* This yields the following ROOTS

c t c t
E     , E     (21.16)
1 s 1 s 1 s 1 s

 The approximation of neglecting all HIGHER states that we have employed here
will be valid as long as the overlap integral s is SMALL

 This corresponds to the case where the coupling between the two wells is WEAK
and the expressions above can then be expanded as

E    ( st  c)  t (21.17)
 Degenerate Perturbation Theory

• Eq. 21.17 shows that the effect of the tunneling integral between the wells is to SPLIT the
energy levels of the two wells

E    ( st  c)  t (21.18)
* It is straightforward to show that the wavefunctions corresponding to these energy
levels can be written as

1
  ( L   R ) (21.19)
2
 As discussed for molecules these are just the BONDING and ANTI-BONDING
states where the anti-bonding state is + and has HIGHER energy

-

E+
E-
+

INDIVIDUAL WELLS AND THEIR GROUND BONDING AND ANTI-BONDING STATES OF THE
STATE WAVEFUNCTIONS COUPLED QUANTUM WELL
 The Variational Method

• The variational method is a specialized approach that may be used to ACCURATELY

estimate the GROUND-STATE energy of a system

* Obviously we know that this ground state has an associated eigenfunction 1 that
must satisfy the Schrödinger equation

H1   11 (21.20)

* If we multiply both sides of this equation by 1* and integrate we obtain

* *
  H     
1 1 1 1 1   1  1*1 (21.21)

* Reorganization of this equation then yields

1 
  H
1 1
(21.22)
*
  1 1
 The Variational Method

• If instead of the eigenfunction 1 we now consider some ARBITRARY wavefunction y that

satisfies the required boundary conditions then the variational principle asserts that
*

1 
  H ( 21.23)
*
 
* To prove the variational principle we start by expressing the wavefunction y in terms
of the TRUE eigenfunctions of the Schrödinger equation

   an n (21.24)
n

* With this substitution the RHS of Eq. 21.23 becomes

* *
 H    a a n n n n
(21.25)
* *
   a a n n n
 The Variational Method

• We thus arrive at the variational principle by noting that the following inequality holds

* * *
aa
n n n n aa
n 1 n n  H
*
 *
 1  1  *
(21.26)
aa n n n aa
n n n  
* The basic idea of the variational method is to GUESS the form of the wavefunction with
a small number of ADJUSTABLE parameters

 These parameters are then adjusted to MINIMIZE the ground-state energy

* As an APPLICATION of this method we estimate the ground-state energy in a

TRIANGULAR well

 We assume the so-called FANG-HOWARD form for the ground state wavefunction
in which the parameter b is allowed to vary FREELY

 1 
 ( x)  x exp  bx (21.27)
 2 
 The Variational Method

• Using the Fang-Howard form the DENOMINATOR of the variational principle yields


*

2 bx 2
 ( x) ( x)dx   x e dx  (21.28)
0 0 b3

* The NUMERATOR is more complicated but can be shown to yield



*  bx / 2  2 2  bx / 2
 ( x) H ( x)dx   xe  2
 eEs  xe
x dx
0   2m x 
0


  2 3  bx 2 6eEs
   bx(1 bx / 4)  eEs x e dx   4 (21.29)
 2 m  4mb b
0

* By dividing Eqs. 21.28 & 21.29 we thus arrive at

 2b 2 3eEs
1   (21.30)
8m b
 The Variational Method

• To minimize the RHS of Eq. 21.30 we differentiate with respect to b and set the
result to zero
2meEs
b6 ( 21.31)
2
* The variational principle may then be expressed as

1/ 3 2 1/ 3 1/ 3
 243   (eEs  )   (eEs  ) 2 
1      2.4764   (21.32)
 16   2m   2m 
 This result should be compared with the EXACT one found previously for the
triangular well
1/ 3
 (eEs  ) 2 
E1  2.3381  
 2m 
VARIATIONAL METHOD AGREES WITH
THE EXACT RESULT TO WITHIN 6%!
 Homework
P21.1 Use variational method for solving the Schrodinger equation for the truncated
harmonic oscillator potential
1 2
V ( x)  kx for x  0
2
  for x  0

Use the trial function x)=xexp(-bx) (b is a variational parameter) to calculate an

approximate value for the ground state energy and compare with the exact result.