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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.
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
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
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)
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.
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.
c n(n 1) x
2
n
n2
(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
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)
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
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.
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
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)
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
d n x2 d n 1 x 2 d n1 x 2
m dx n
H e dx H
m dx n 1
e
m dx n1 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.
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 m1 e x2
dx
dx n 1
d n m x 2
H n H me dx 2 (1) (m!) H 0
x2
(1) n m m
e dx mn (C )
dx n m
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 nm x 2
H dx 2 (1) (m!) H 0 n m e dx
x2
(1) n
n H me m m
mn
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 nex
2
/2
(23)
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 ne x
2
/2
H n ' Zn 'ex Z n xe x
2 2
/2 /2
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.
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)
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)
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 )
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.
Aung, Pye, Phyo. "Application of Hermite Polynomials in the Quantum Simple Harmonic
Oscillator." Physical Chemistry I Legacy Project