Time Dependent Schrdinger Equation

Up until now we have been talking about stationary states which dont change with
m , but recall that the state function
f
is also a f
function of
f time,
m , (q
(q1,,... qn, t)) in
time,
general. When will we care about time dependence? Most of the time! For
examples,
spectroscopy molecule interacting with electromagnetic radiation
and implies transitions between states.
states
chemical reactions imply transitions between at least two states.
The time evolution of a state function is g
given by
y Postulate V, which says
y that the
state function satisfies the simple appearing differential equation:

(x, t)

H (x, t) = i =
t

is the Hamiltonian operator. So we must solve this equation.

and H
We will do so by means of Separation of Variables. This is a very important
technique,
q
one that we shall use again
g
and again.
g
Essentially
y no problem
p
is solvable
unless we can separate variables. Note carefully the logic in what follows:
First, assume that (x, t) is a the product form (x, t) = (x) f(t)
We then try to solve the Schrdinger equation with such a separable form.
form If we
succeed in finding a general solution with this restrictive assumption, then we
have justified our separability assumption, and all is well.

So, making this assumption,the Schrdinger equation becomes

(x) f(t)
f(t)
d f(t)

= (x) i =
= (x) i =
H( (x) f(t)) = i =
t
t
dt

So, with this assumption, the right side of the above equation simplifies as
above.,
contains no explicit time dependence, then f(t) is also a
Now, if in addition,H
, and
constant
t t with
ith respectt tto th
the actions
ti
iindicated
di t d b
byH
d f(t) can b
be b
brought
ht
operator.
through theH
to have no time dependence?)
(What does it mean forH

In any
y event,, we obtain

f(t)

f(t)H (x) = (x) i=

t

an equation which we need to solve.

There are basically two standard things one should always think about (as before):
No. 1 Divide by written in product form [Here it is (x)f(t)]
No
No. 2
2 Multiply by
* and integrate.
integrate
(We used both earlier in the proof of properties of Hermitian operators.)

After applying
pp y g No. 1, we have

f(t)
(x)
f(t)
i=
H (x) =
f(t) (x)
f(t) (x)
t
or
i = f(t)
H (x)
=
(x)
f(t) t

(as before, why cant I cancel out on the left side ??)
Notice that the left side is a function of x only and the right side is a function
of t only.
only
Thus we have that b(x) = g(t) for all x and all tt. This can only
be the case if
b(x) = constant = g(t)
Call the constant something convenient. Since units are energy, call it E. Then

H (x)
=E
(x)
and
i = df(t)
E=
f(t) dt
Look at (b)
iE
df(t)
=
f(t)
=
dt

Integrate this equation to obtain

f (t) = e

i Et
=

for the time dependence of (x,t).

(a)

(b)

The spatial dependence comes from solving equation (a), rewritten as

H (x) = E (x)
,

a relation that we recognize as the total energy eigenvalue equation. This is exactly
the equation that we solved earlier to obtain the energy states of the particle in a
box! This total energy eigenvalue equation is best known as the

Time Independent Schrdinger Equation

The existence of a p
product form solution enabled the one differential
equation in two variables to be written as two separate differential equations, each
having only one variable. This is useful because we can kill any differential equation
in one variable with only computing and no thinking.
This concept is very important and will occur again and again.

A final point for your consideration. Consider what the state function looks like
if we are in an energy eigenstate
eigenstate, say En, with spatial dependence n.
The full state function is (x, t) = n(x) e-iEnt/= , with a complex time
dependence!
However, the probability density P is given by * ,

P = * = n*(x)e
(x)eiEnt/= n(x)e-iEnt/= =
*n(x) n(x)
There is no time dependence in the probability density.
This is a property
t of
f an eigenstate
i
t t or a stationary
t ti
state.
t t
For an eigenstate m, probability densities and average values are timeindependent!
p
But for a state function that is not an eigenfunction,
g
,
* dx will depend on time.

After assuming a product form solution

(x,t) = (x) (t), the TDSE becomes

1 = 1
i=
=
+
V
=
E
2
t 2m x
2

If the potential energy function V in the Schrdinger

Equation is a function of time, as well as x, [V = V(x,t)]
p
of variables still work;; that is,, would
would separation
there still be solutions to the SE of the form
(x,t) = (x) (t)?
A) Yes, always B) No, never
C) Depends on the functional dependence of V
on x and t

TIME DEPENDENCE of
Now we have seen how to separate variables and obtain a
solution to the above equation when the state function could
be written as a product,
product (q,t)
(q t) = (q)f(t). We saw that
*(q,t)(q,t) was NOT a function of time when (q) was an
eigenfunction of H .
We demonstrate
m
a more
m
general
g
solution,, but one still
restricted to the case that does not contain explicit time
dependence This restriction allows us to view the propagation
dependence.
of a wave packet and make additional connection with our
i
intuitive
i i understanding.
d
di
W demonstrate
We
d
a solution
l i f
for a two
term form, but the general result will be obvious.

TIME DEPENDENCE of
Let 1(x) and 2(x) be eigenfunctions of

with eigenvalues E1 and E2

respectively. Consider the following state function s(x, t)

s ( x, t ) = 1(x) e

iE1 t
=

+ 2(x) e

iE2 t
=

We will show that it is a solution to the time dependent Schrdinger equation.

s (x, t)

H s (x, t) = i =
t
does not depend upon time, then the left side of the time-dependent
If H
Schrdinger equation can be expanded as

-iE1t
-iE 2t

H s ( x, t ) = E 1 1(x) exp
+ E 2 2(x) exp
h
h

-iE
-iE
1t
2t

H s ( x, t ) = E 1 1(x) exp
+ E 2 2(x) exp
h
h
and the right side as the following:
s(x, t)
iE1 t
iE 2 t
iE1
iE 2
+i =
i=
=i=
1((x)) expp
2((x)) expp

t
=
=
=
=

iE 2 t
iE1 t
+ E 2 2 ((x)) exp
= E1 1 ((x)) exp
p
p
=
=

Since the two sides are identical, this sum of products form
is a solution to the time dependent Schrdinger equation
wheneverH has no time dependence.
Note that now *s(x, t) s(x, t) has time dependence.
i ( E E )t
i ( E1 E2 )t
1 2

*s s = 12 ( x ) + 22 ( x ) + 1 2 e

+ 1 2 e

( E1 E2 ) t
= ( x ) + ( x ) + 1 2 cos

2
1

2
2

Use Mathcad to see some other examples of acceptable state functions for the
particle in a box. Let the box extend from 0 to . Consider a state function
which is the sum of the first 100 eigenfunctions.
Set ranges for x and n.
n
n=1, 2, . . . 100 0 < x <
Define the eigenfunctions.
2.

f( x , n )

sin( n. x )

Are the f(x,n)

f(x n) orthogonal? Normalized? Check one numerically!

f( x , 4 ) dx = 1
0
YES!
Now define our 100 term function, g(x).

100
g( x )

0.1.

f( x , n )
n= 1

Is it normalized?

What does the state function look like? Is it an acceptable state function?

and what is the probability density?

g( x )

2 20

0.2
x

What is the average kinetic energy? How does it propagate in time?

How does this relate to the so-called function?? Also, if we set
E1=1,, then En = n2, and we easily
y find E as

E =

How would this state function evolve in time?

0.4

Lets look at an example.

Consider the evolution of a localized particle on the left side of a box.

First we construct a state function localized on the left side
First,
of the box. We could put a Gaussian or some such function
on the left side of the box, with whatever width we choose.
`A
A simpler way to get a feeling for this is to employ the sum
of the first 10 particle in a box eigenfunctions as our initial state.
The box extends from x = 0 to x =1. We construct the time dependent
state f
function with the f
first 10 eigenfunctions
g f
having
g equal
q
weight.
g
10

b g

Thus s ( x, t ) = 2 sin j x e

iE jt
=

j=1

The individual components are all in phase at t = 0.

This will give a peak near the left side of the box at tt=0.
0.
What do the individual components look like?
We then p
propagate
p g
the function in time, using
g the expression
p
above.

Ti D
Time
Dependence
d
off
The iinitial
Th
iti l state
t t iis th
the sum off th
the
first 10 particle in a box
eigenfunctions.

The box extends from 0 to 1

We construct
W
t t the
th ti
time d
dependent
d t state
t t
function with all of the first 10
eigenfunctions having equal weight
They are all in phase at t = 0. This will give
a peak near the left side of the box at t=0.
t=0
What do the individual components look
like?
We then propagate the function in time,
using the expression from notes.

Individual components of

t=0

t = 0.01
0.12

0.12

0.1

0.08

f( x , t ) . f( x , t ) 0.06

0.04

0.02
0

0
0
0

0.2

0.4

0.6
x

0.8

1
1

t=0.02

t = 0.03

t = 0.04

t = 0.05

t = 0.06

t = 0.07

t = 0.08

t = 0.09

t=0.1

t=0.125

t=0.15

t=0.175

t = 0.2

t = 6.283 Note recurrence!