Quantum Explanations – Issue I

- Quantum Mechanical Harmonic Oscillator

Author: Ryan Jadrich

Last Update: December 1, 2007

Introduction: Your every day Harmonic oscillator is a fairly simple problem to describe
and model by simple easily solvable differential equations. On the other hand the
quantum mechanical harmonic oscillator is at a much higher degree of difficulty in terms
of understanding it and solving the necessary differential equations to model it. Most
texts will simply give the ordinary harmonic oscillator differential equation and then
move onto the differential equation describing that of the quantum version. Finally they
will state that the solution is too difficult to work out and they will only give you the
answer. This is lazy and if you can understand quantum mechanics you can probably
understand the math behind the solutions. This is only one of the many occasions for this
in quantum mechanics and other issues will cover different topics in all of the gruesome
detail that anyone could ever want.

Explanation:

Part I. – First off we will consider that of a harmonic oscillator composed of two masses
attached by a spring because it turns out that to a reasonable approximation the bonds
holding molecules act in a nature like that of a spring.

Figure I. – The two mass spring scenario

If the spring is a normal spring then this system will be described by two separate
differential equations, one for the first mass and one for the second mass. Since the force
on the separate masses only depends on the relative displacement from the rest length l 0
the equations for the two masses are exactly the same except the negative sign. This is
due to the fact that the force on one mass will always be opposite that of the other mass.

d 2 x1
m1  k ( x 2  x1  l 0 ) (1)
dt 2
d 2 x2
m2 2   k ( x 2  x1  l 0 ) (2)
dt

Copyright © Ryan Jadrich 2007 -1-

Since the motion is governed only by that of the relative displacement between the
masses (atoms) we want to get a differential equation describing that of the relative
distance. This can be done by subtracting equation one from equation two and the result
of this is given below. Note that in the derivative only the x variables are needed as in
differentiation the constant l 0 would just disappear.

d 2 ( x 2  x1 ) 1 1
2
 k (  )( x 2  x1  l 0 ) (3)
dt m1 m2
d 2x 1 1
2
 k (  )x (4)
dt m1 m2

The next step is to take the messy expression involving the masses and define something
referred to as the reduced mass which is represented by  which makes the expression a
little neater.

1 1 1
 
 m1 m2
m1m2

m1  m2
d 2x 1
 k ( ) x
dt 2

d 2x
  kx  0 (5)
dt 2

By golly that looks just like the differential equation describing the motion of a ordinary
harmonic oscillator. So from any differential equations course the solution to this
equation can easily be shown to be in its most general form as:

x  c1 cos(t )  c 2 sin(t )
k


1 1 k
v 
2 2 

Copyright © Ryan Jadrich 2007 -2-

Part II. – Here comes the cool stuff where we apply this to a quantum system where
really tiny stuff don’t behave the way they should. The best place to start of is stating that
in order to describe this system the use of the Schrödinger equation is needed and is
stated below in its one dimensional form.

 2 d 2
  V ( x)  E (6)
2m dx 2

For those who want a review the V(x) is the potential on a particle, the E is the energy
which is taken to be a constant, the  is the wave function for a particle which describes
not is absolute position but rather describes its probability of being found at a location as
a continuous function of x. finally the m is the mass of the particle and the  is the
reduced plank constant.

The next part is to substitute the various conditions for our reduced mass system
undergoing simple harmonic motion. In this case we have to substitute the spring
potential energy function for V(x) and  for the mass and finally we will have our
differential equation describing a quantum mechanical harmonic oscillator. This is given
below with all substitutions.

m
1 2
V ( x)  kx
2
 2 d 2 1 2
  kx   E ( 7)
2  dx 2 2

This equation is a real pain in the neck to solve. The good thing though is that it certainly
looks similar to another differential equation that we do have a solution for which is
referred to as Hermite’s differential equation. The comparison of equation 7 in a rewritten
form (8) with Hermite’s diffq (9) is given below for your visual inspection.

 2mE kx 2 
 ' ' 2  2   0 (8)
   

y ' '2 xy '2my  0 (9)

From the similarities we can assume that (8) will have solutions at least similar to that of
(9) which we know and will show you how to solve. The solution to (9) is not in the form
of a nice equation but rather a series of terminating polynomials that stem from a power
series solution.

Copyright © Ryan Jadrich 2007 -3-

Our first step in solving Hermite’s differential equation is substituting in the general form
of a power series which is shown below.


y   cn x n (10)
0

Since the first and second derivatives also appear in the equation we will be needing
those which are easily found by differentiation of (10). The summation indexes are each
shifted up by one for each derivative because the first and corresponding second terms
will be zero.


y '   c n nx n 1 (11)
1

y ' '   c n n(n  1) x n  2 (12)
2

Now that we have our necessary derivatives we can plug them into Hermite’s differential
(9) equation and in the second term we can multiply through by x and in all terms move
any constant coefficients into the summation.

  

 cn n(n  1) x n2  2 x cn nx n1  2m cn x n  0

2 1 0
  

 c n(n  1) x
2
n
n2
  (2c n n) x n   (2mc n ) x n  0
1 0
(13)

Now we have a problem. We want to add up the necessary series and form one unique
series that will lead to our solution. The problem is that the equations do not start with the
same powers of x, so we have to take out the necessary amount of terms from each. For
this example we will want all of the summations to start at a power of 1. This means we
will have to take out one term from equation (13) in the first and last summations so that
they start at one like the middle summation. The adjusted equation is given below.

  
2c 2   c n n(n  1) x n  2   (2c n n) x n  2mc0   (2mc n ) x n  0 (14)
3 1 1

Copyright © Ryan Jadrich 2007 -4-

Now that we have the summations all beginning with the same power of x we have to use
what is called a k substitution to get the summations to not only begin with the same
power but with the same index number. In the first summation we set k=n-2. The second
summation k=n, and the third k=n again. Then we change all n’s into their corresponding
k forms including the summation starting value. If you are unsure of this method look up
adding together power series and you should find a really simple explanation of this
valuable technique.

  
2c 2   c k  2 (k  2)(k  1) x k   (2c k k ) x k  2mc0   (2mc k ) x k  0 (15)
1 1 1

Now our equation not only starts with the same power but with the same index and now
our power series can be added together into one big conglomerate as given in equation
(16) below.


2c 2  2mc0   [c k  2 (k  2)(k  1)  2c k k  2mc k ]x k  0 (16)
1

From (16) we get two separate equations that must be equal to zero in order for the
expression to be true. The constant out front must sum to zero, and the constants inside
the brackets inside the summation must equal zero as this must hold true for all x.

2c 2  2mc0  0
c 2   mc0 (17)

c k  2 (k  2)(k  1)  2c k k  2mc k  0
2(k  m)
ck  2  c k , k  1,2,3,... (18)
(k  2)(k  1)

Copyright © Ryan Jadrich 2007 -5-

From equations (17) and (18) we have what is referred to as a recursion relation which
means we will be able to get a series in terms of the unknown constants c0 and c1 . The
first values of c are given below.

c0  c0 , c1  c1

c 2   mc0

2(1  m) 2(1  m)
c3  c1  c1
(1  2)(1  1) 3!
2(2  m) 2 2 (2  m)( m)
c4  c2  c0
(2  2)(2  1) 4!
2(3  m) 2 2 (3  m)(1  m)
c5  c3  c1
(3  2)(3  1) 5!
2(4  m) 2 3 (4  m)(2  m)( m)
c6  c4  c0
(4  2)(4  1) 6!
2(5  m) 2 3 (5  m)(3  m)(1  m)
c7  c5  c1
(5  2)(5  1) 7!

Now that we have are coefficients to equation (10) we can plug in and get our general
solution to Hermite’s differential equation.


y   cn x n
0

 2 2 (2  m)( m) 4 2 3 (4  m)(2  m)( m) 6 

y  c0 1  ( m) x 2  x  x  ... (19)
 4! 6! 
 2(1  m) 3 2 2 (3  m)(1  m) 5 2 3 (5  m)(3  m)(1  m) 6 
 c1  x 1  x  x  x  ...
 3! 5! 7! 

This general expression can be written as two separate solutions that we will use based on
whether or not the number m is and even or odd integer.

 2 2 (2  m)( m) 4 2 3 (4  m)(2  m)( m) 6 

y  c0 1  ( m) x 
2
x  x  ... (20)
 4! 6! 
 2(1  m) 3 2 2 (3  m)(1  m) 5 2 3 (5  m)(3  m)(1  m) 7 
y  c1  x1  x  x  x  ... (21)
 3! 5! 7! 

Copyright © Ryan Jadrich 2007 -6-

It can be easily seen if the integer m is even then (20) will terminate with the highest
power equal to that even integer, and the opposite is true for (21). So if m is an even
integer we take (20) as our solution and if m is odd we take (21) as our solution. Given
below are the first few solutions for various integers of m and then immediately next to
the solution is a scaled version of the polynomial which is called the Hermite
polynomials. This is done to make them look pretty really, and this can be done as any
constant multiple times the polynomials will be solutions to (9).

m  0, y  1, H0 1

m  1, y  x, H1  2x

m  2, y  1  2x 2 , H 2  22 x 2  2

4 3
m  3, y  x x , H 3  2 3 x 3  12 x
3!

2 2 (8) 4
m  4, y  1  4x 2  x , H 4  2 4 x 4  48 x 2  12
4!

Now before we move onto applying this result to the quantum mechanical harmonic
oscillator we are going state two formulas with out proof. The first is a relationship that
can be used to generate the Hermite Polynomials as shown above using:

d n  x2
H n  (1) n e x
2
e ( A)
dx n

The next relationship relates the Hermite polynomials of different order,

d
H n  2nH n 1 ( B)
dx

Part III. – Finally we will solve the Schrödinger equation for a simple harmonic
oscillator. This is the really fun stuff. Lets bring back are two equations which are again
stated below.

 2mE kx 2 
 ' ' 2  2   0 (8)
   

y ' '2 xy '2my  0 (9)

Copyright © Ryan Jadrich 2007 -7-

We now know the solutions to equation (9) in terms of the Hermite polynomials. Since
(8) and (9) look so much alike it might be possible to solve (8) with some form of
Hermite polynomials. Let’s try. The first major problem is that Hermite polynomials are
not orthogonal to one another unless a weighing function is brought into play. This is
demonstrated below.

H

n H m dx  0

With the appropriate weighing function though the polynomials will be orthogonal as
demonstrated below.

H H m e  x dx  0
2

n


(22)


H H n e  x dx  2 n n! 
2

n


Now to prove these relationships we will be using relationship (A) for our Hermite
polynomial of order n in (22). Doing so we get,

 
d n  x2
 H n H me dx   H m
x2
(1) n
e dx
  dx n

Then after integration by parts once we are left with,


 
d n  x2  d n 1  x 2  d n1  x 2
 m dx n

H e dx   H
 m dx n 1

e 
   m dx n1 e dx
  
H '

It is easy to se that the portion outside of the integral is equal to zero because of the
weight function which when differentiated any number of times will go to zero at both
limits of infinity.

Now we can use Relationship (B) in our new equation to get,

 
d n 1  x 2
(1) n  H n H m e  x dx    H m '
2
e dx
  dx n 1
 n 1
d
 2(1)1 m  H m1 e x2
dx
 dx n 1

Copyright © Ryan Jadrich 2007 -8-

Now it is clear that if we perform integration by parts m times we will be left with,

 
d n m  x 2
 H n H me dx  2 (1) (m!)  H 0
 x2
(1) n m m
e dx mn (C )
  dx n m

Now if m=n the last expression (C) will be,

 

 H m H m e dx 2 (1) (m!)  e dx
x m m m
2
x 2

 

 2 (1) (m!) 
m 2m

 2 m (m!) 

Which proves the second part of (22) except in terms of m. In the case that m does not
equal n then (C) can be integrated one more time to obtain,

 
d nm  x 2
H dx  2 (1) (m!)  H 0 n m e dx
x2
(1) n
n H me m m
mn
  dx

d n m 1
 2 (1) (m!) n m 1 e  x 0
2
m m

dx 

This proves the first part of (22). Now we continue on to solving our equation.

Since the solutions of (8) must be orthogonal to one another it seems that we should
define a new function based on (22) which includes the Hermite polynomial and a portion
of the weighing function. This is defined as:

Z n  H nex
2
/2
(23)

Then by rearranging (23) we get:

H n  Z ne x
2
/2
(24)

Since (24) is a solution to (9) we will take all necessary derivatives of (24) and substitute
the results into (9) to get a new differential equation.

H n  Z ne x
2
/2

H n ' Zn 'ex  Z n xe x
2 2
/2 /2

H n ' Z n ''e x  Z n ' xe x  Z n ' xe x  Z n [e x  x2e x

2 2 2 2 2
/2 /2 /2 /2 /2
]

Copyright © Ryan Jadrich 2007 -9-

Now that we have all necessary derivatives we can just plug them all into Hermites
differential equation and get a new differential equation.

H n  Z ne x
2
/2

H n ' Zn 'ex  Z n xe x
2 2
/2 /2

H n '' Zn ''e x  Z n ' xe x  Z n ' xe x  Z n [e x  x 2e x

2 2 2 2 2
/2 /2 /2 /2 /2
]

y ' '2 xy '2my  0 (9)

Z ' ' e  Z ' xe

n
x2 / 2
n
x2 / 2
 Z n ' xe x
2
/2
 Z n [e x
2
/2
 x 2e x
2
/2
 
]  2x Z n ' e x
2
/2
 Z n xe x
2
/2

 2mZ e  02
x /2
n (25)

After simplifying (25) a bit and rearranging terms we will end up with an equation that
look strikingly similar to that of equation (8) which we are trying to solve. The
comparison is given below.

Z n ' ' ((2m  1)  x 2 ) Z n  0 (26)

 2mE kx 2 
 ' ' 2  2   0 (8)
   

The only issue with our equations is that in (8) we are lacking a coefficient of one in front
of the x squared term. If we could only make (26) look identical to (8) we would have our
solutions and be able to determine or energy relationship. To do this we need to define a
new wave function in terms of a new variable that will satisfy (26).

 ( p)   ( x) (27)

p  x (28)

 ( x)   ( p /  )   ( p)

Copyright © Ryan Jadrich 2007 - 10 -

With are new expressions we will need the necessary second derivative of are new
function to substitute into (8). This is worked out below.

d ( x) dx d ( p )
 
dx dp dp
d
  ' [ p /  ]  '
dp
d ' dx d '
   (1 /  ) 
dx dp dp
  ' ' (1 /  ) 2   ' '
  ' '   2 ' ' (29)

Our next step is to substitute equations (27), (28), and (29) into (8) to get an equation in
terms of our new wave function.

 2mE kp 2 
 2  ' ' 2  2 2   0
    
 2mE kp 2 
 ' ' 2 2  4 2   0 (30)
    

Now that we have this extra constant multiple which can by the way we defined it to be
anything we have an extra degree of freedom in the manipulation of our differential
equation. We will choose it so that it makes the constant in front of the p squared term
equal to one.

k
1
 4 2
mk
2  (31)


Then after plugging in alpha (31) we will get the differential equation below.

 2E m 
 ' '  p 2   0 (32)
  k 

Now comparing (32) with (26) we shockingly see that they are identical.

 2E m 
 ' '  p 2   0 (32)
  k 
Z n ' '((2m  1)  x ) Z n  0
2
(26)

Copyright © Ryan Jadrich 2007 - 11 -

Therefore equation (32) has the same solutions as in (26) which is the product of a
Hermite polynomial and a portion of the necessary weighing function to make different
polynomials orthogonal to one another. If this were not true then the wave function
would not approach zero at infinity and the probability of finding a particle in a localized
region would be zero and this can’t be.

So are solutions are given below:

Z n ( p )  H n ( p )e  p
2
/2

Z n ( x)  H n (x)e 
2 2
x /2
(33)

( k )1 / 4
  1/ 2


The next bit is about the factor needed to normalize the solutions. This normalized wave
function is stated below,

 norm  (2  m / 2  1 / 4 (m!) 1 / 2 ) Z n ( x)
 (2  m / 2  1 / 4 (m!) 1 / 2 ) H n (x)e 
2 2
x /2
(34)

To prove this we will use the expression that we already proved which states that,

H H m e  x dx  2 m (m!) 
2

m


Now using the Z functions which are our solutions that are stated in (33) we will attempt
to normalize these functions.

 
A 2  Z m Z m dx  A 2  H m (x)e  H m (x)e  dx  1
2 2 2 2
x /2 x /2

 


 H m (x) H m (x)e

A dx  1
2 2
2 x



 A 2 (2 m )(m!)   1
1
 A
(2 m )(m!) 
 A  (2 m / 2  1 / 4 (m!) 1 / 2 )

Copyright © Ryan Jadrich 2007 - 12 -

Which is precisely the normalization coefficient that we had hoped for? With this
normalization,

  norm 1
2



And this is exactly what we wanted. So all in all our solutions are given by (34), and
these give the probability amplitudes for a quantum mechanical harmonic oscillator.

The last bit refers to the energy levels of the quantum mechanical harmonic oscillator.
The allowed energy Eigen-values can be figured out by comparing equation (32) and (26)
and by noting that m must be an integer to get this Hermite polynomial like solutions.

2E 
 2m  1
 k
1 k
E  ( n  )
2 
1
E  (n  ) (35)
2

From (35) it can easily be seen that the energy can only take on certain values as is
expected of a quantum system.

Sources:

Silbey, Robert J., Robert A. Alberty, and Moungi G. Bawendi. Physical Chemistry. 4th ed.
Wiley, 2005.

Pahikkala, J.. "Hermite polynomials." PlanetMath.org. October 10 2006 .

PlanetMath.org. 1 Dec 2007
<http://planetmath.org/encyclopedia/HermitePolynomials.html>.

Aung, Pye, Phyo. "Application of Hermite Polynomials in the Quantum Simple Harmonic
Oscillator." Physical Chemistry I Legacy Project

Copyright © Ryan Jadrich 2007 - 13 -