Ch40 Young Freedmanx

Chapter 40/41: Quantum Mechanics
Wave Functions & 1D

Schrodinger Eq
Particle in a Box
Wave function
Energy levels
Potential Wells/Barriers &
Tunneling
The Harmonic Oscillator
The H-atom
Quantum Wave Function
In QM, the matter wave postulated by de Broglie is described by a complex-
valued wavefunction +(x,t) which is the fundamental descriptor for a quantum
particle.
x,t
Re/Im +(x,t)
+(x,t) is a complex-valued function of
space and time.
1. Its absolute value squared
gives the probability in finding the
particle in an infinitesimal volume dx
at time t.
2. For any Q problem:
The goal is to find for the
particle for all time.
Physical interactions involves
operations (A) on this wave
function:
Experimental measurements will
involve the products,
2
( , ) x t dx +
( , ) x t +
( , ) A x t +
( , ) A x t + ( , ) x t
-
+
Since is a probability, it has to be normalized !
Wave Function and Probability
2
*
( , ) ( , ) ( , ) x t x t x t + = + +
is the probability distribution function (or probability density)
In other words,
2
+
x dx
is the probability in finding the particle in
the interval at time t. [ , ] x x dx +
(shaded area)
2
( ) ( , ) p x dx x t dx +
2
( ) ( , ) 1 p x dx x t dx
+ +

= + =
} }
(At any instance of time t, the particle must be somewhere in space !)
2
( , ) x t dx +
(Similar to the intensity of an electric field:
being proportional to the #of photons.)
2
I E
The Schrodinger Equation
In Classical Mechanics, we have the Newtons equation which describes the
trajectory x(t) of a particle:
m = F x
In EM, we have the wave equation for the propagation of the E, B fields:
2 2
2 2 2
, 1 , E B E B
x c t
c c
=
c c
(derived from Maxwells eqns)
In QM, Schrodinger equation prescribes the evolution of the wavefunction
for a particle in timet and space x under the influence of a potential energy U(x),
2 2
2
( , ) ( , )
( ) ( , )
2
x t x t
U x x t i
m x t
c + c+
+ + =
c c
(general 1D Schrdinger equation)

U(x)
Now, from the de Broglie relations, the energy and momentum of this
quantum free particle must be related to its wave number and angular
frequency through:
Since the reference point for is arbitrary, we can simply take .
Then, the energy E of a free particle will simply be its kinetic energy,
Wave Equation for a Quantum Free
Particle
A free particle has no force acting on it. Equivalently, the potential energy
( ) U x
e
k
( )
0
x
F dU x dx = =
( ) U x
( ) 0 U x =
2 2 2
2
1
2 2 2
m v p
E mv
m m
= = =
must be a constant for all x, i.e.,
2
2
h
E hf f t e
t
= = =
2
2
h h
p k
t
t
= = =
2 2
2
k
m
e =

2
2
p
E
m
=
(non-relativistic)
We now assume the fundamental sinusoidal form for a wave function of a
quantum free particle with mass m, momentum and energy :
Particle
Thus, a correct quantum wave function for this free particle must satisfy this
quantum dispersion relation for and :
e k
E e =
( )
2 2
*
2
k
m
e =

p k =
(non-relativistic)
( )
( )
( ) ( )
, cos sin
i kx t
x t Ae A kx t i kx t
e
e e
+ = = + (

Particle
Substituting the trial solution into the Schrodinger's
Equation, we have,
( )
( )
( )
2
2 2
2
2
,
2 2
i kx t
x t
A ik e
m x m
e
c +
(
=

c

( )
( )
( )
,
i kx t
x t
i i A i e
t
e
e

c+
(
=

c

( )
( )
,
i kx t
x t Ae
e
+ =
( )
2 2
2
i kx t
k
Ae
m
e
(
= +

( ) i kx t
Ae
e
e

(
= +

LHS:
RHS:
( for a free
particle)
( ) 0 U x =
Particle
Thus, yes indeed! The proposed quantum wave function for a free particle
( ) ( )
2
2
2
, ,
2
x t x t
i
m x t
c + c+
=
c c
is a solution of the 1D Schrodingers Equation,

2 2
2
k
m
e =
( )
( )
,
i kx t
x t Ae
e
+ =
and it satisfies the required quantum dispersion relation:
The 1D Schrodinger Equation
As we have see,
- the first term (2
nd
order spatial derivative term) in the Schrodinger equation
is associated with the Kinetic Energy of the particle
- the last term (the 1
st
order time derivative term) is associated with the total
energy of the particle
- together with the Potential Energy term U(x)+ (x)
the Schrodinger equation is basically a statement on the conservation of
energy.
KE PE Total E + =
2 2
2
( , ) ( , )
( ) ( , )
2
x t x t
U x x t i
m x t
c + c+
+ + =
c c
In fact, in general, we have,

Stationary States
For most problems, we can factor out the time dependence by assuming the
following harmonic form for the time dependence,
( , ) ( )
i t
x t x e
e

+ =
(Recall the free particle case: .)
( , )
ikx i t
x t Ae e
e
+ =
With , we can rewrite the time exponent in terms of E,
/
( , ) ( )
iEt
x t x e

+ =

/ E e =
is a state with a definite energy E and is called astationary state. ( , ) x t +
Note that,
2
* * / /
( , ) ( , ) ( , ) ( ) ( )
iEt iEt
x t x t x t x e x e
+ = + + =

2
* ( / / ) *
( ) ( ) ( ) ( ) ( )
i Et Et
x x e x x x
+
= = =

( ) x
is called the time-independent wave function.
The Time-Independent Schrdinger
Equation
Substituting this factorization into the general time-dependent Schrodinger
Eq, we have
( )
/ / /
( , )
( ( ) ) ( )
iEt iE iE t t
x t iE
i i i x x e E x e e
t t

c+ c
| |
= = =
|
c c
\ .

and,
2 2
2 2
/
( , ) ( )
iEt
x t d x
e
x dx

c +
=
c

RHS
LHS
2
/
2
2
( )
2
iEt
d x
e
dx m
/
( ) ( )
iEt
x e U x

+
/
( )
iEt
E x e

=

2 2
2
( )
( ) ( ) ( )
2
d x
U x x E x
m dx
+ =
(time dependence can

be cancelled out !)
More on Wavefunction
In general, the probability in finding the particle in the interval [a,b] is given
by:
2
( )
b
ab
a
p x dx =
}
Note: is not the probability density
is the probability density.
( ) x
Other physical observables can be obtained from (x) by the following operation:
2
( ) x
a b
x
p(x)
example (position x):
2
( ) ( ) x xp x dx x x dx

= =
} }
is called the expectation value (of x): it is the experimental
value that one should expect to measure in real experiments !
x
More on Wavefunction
In general, any experimental observable (position, momentum, energy, etc.)
O(x) will have an expectation value given by:
2
( ) ( ) O O x x dx
=
}
Expectation values of physically measurable functions are
the only experimentally accessible quantities in QM.
Wavefunction itself is not a physically measureable
quantity.
( ) x
Note:
O can be x, p, E, etc.
Standard Procedure in Solving QM
Problems with Schrodinger Equation
(with the time-independent Schrodinger Equation)
Given: A particle is moving under the influence of a
potential U(x).
Examples:
Free particle: U(x) =0
Particle in a box:
Barrier:
HMO:
0, 0
( )
,
x L
U x
elsewhere
s s
0
, 0
( )
0,
U x L
U x
elsewhere
s s
2
1
( ) '
2
U x k x =
Standard Procedure in Solving QM
Problems with Schrodinger Equation
Solve time-independent Schrodinger equation for (x) as a function of energy E,
with the restrictions:
and are continuous everywhere for smooth U(x).
is normalized, i.e.,
Bounded solution:
( ) x
( ) d x
dx
( ) x
2
( ) 1 x dx
=
}
( ) 0 x as x
Then, expectation values of physical measurable quantities can be calculated.
Particle in a Box
A 1-D box with hard walls:
(0) ( ) U U L = = (non-penetrable)
A free particle inside the box:
( ) 0 U x = (inside box)
No forces acting on the particle
except at hard walls.
P (in x) is conserved between
bounces
|P| is fixed but P switches
sign between bounces.
Classical Picture
Particle in a Box (Quantum Picture)
The situation can be described by the following potential energy U(x):
0, 0
( )
,
x L
U x
elsewhere
< <
2 2
2
( )
( ) ( ) ( )
2
d x
U x x E x
m dx
+ =
The time-independent Schrodinger equation is:

Recall, this is basically
KE PE Total E + =
Problem statement: For a given U(x), what are the possible wave functions (x)
and their corresponding energies E ?
Inside the box, , U(x) =0, and the particle is free. From before,
we know that the wave function for a free particle has the following form:
Wave functions for a Particle in a Box
0 x L < <
1 2
( )
ikx ikx
inside
x A e A e

= +
(linear combination of the two
possible solutions.)
where A
1
and A
2
are constants that will be determined later.
Outside the box, , and the particle cannot exist outside the box and ( ) U x =
( ) 0
outside
x = (outside the box)
At the boundary, x =0 and x =L,the wavefunction has to be continuous:
(0, ) (0, ) 0
inside outside
L L = =
2 2
2
k
E
m
| |
=
|
\ .
Wavefunctions for a Particle in a Box

Let see how this boundary condition imposes restrictions on the two
constants, A
1
and A
2
, for the wave function.
Using the Eulers formula, we can rewrite the interior wave function in terms
of sine and cosine:
( ) ( )
( ) ( )
1 2
1 2 1 2
( ) cos sin cos sin
cos sin
inside
x A kx i kx A kx i kx
A A kx i A A kx
= + +
= + +
Imposing the boundary condition at x =0,
( ) ( )
1 2 1 2
(0) cos0 sin0
inside
A A i A A = + +
( )
1 2
0 A A = + =
1 2
A A =
1
( ) 2 sin sin
inside
x iA kx C kx = =
(where C=2iA
1
)
ikx
e
+
ikx
e
Wavefunctions for a Particle in a Box

Now, consider the boundary condition at x =L:
( ) sin 0
inside
L C kL = =
For a non-trivial solution ( ), only certain sine waves with a
particular choice of wave numbers (k) can satisfy this condition:
0 C=
or , 1,2,3,
n n
n
k L n k n
L
t
t = = =
This implies that the wavelengths within the box is quantized !
2
2
n
n
k
t
t = =
L
nt
2
, 1,2,3,
L
n
n
= =
Allowed wavelengths are the ones which can fit within the box !
Wavefunction for a Particle in a Box
2 2
, 1,2,3,
n
n
L
n
k n
t
= = =
/ 2
3 / 2
L must fit an integral number of
half-wavelengths: 2
n
L n =
Then,
( )
( ) sin sin ,
1,2,3,
n n
n
k
L
x C x C x
n
t
| |
= =
|
\ .
=
(similar to standing waves on a cramped string)
2
5 / 2
, 1,2,3,
n
n
k n
L
t
= =
Or,
Quantized Energies for a Particle in a
Box
Since the wave number k
n
is quantized, the energy for the particle in the box is
also quantized:
2
2 2 2 2 2 2 2 2
2 2
or , 1,2,3,
2 2 2 8
n
n
k n n n h
E n
m m L mL mL
t t | |
| |
= = = = =
| |
\ .
\ .

Note: the lowest energy

is not zero:
2
1
2
0
8
h
E
mL
= >
n =0 gives (x) =0
and it means no particle.
(n is called the
quantum number)
Probability and Wavefunction
Recall that | (x)|
2
(and not the wavefunction itself (x)) is the probability
density function. In particular,
2
2 2
( ) sin
n x
x dx C dx
L
t
=
gives the probability in finding the particle in an interval [x, x+dx] within the box.
Probability in Finding the Particle
Notes:
The positions for the particles are
probabilistic. We just know that it
has to be in the box but the exact
location within the box is uncertain.
Not all positions between x =0 and
L are equally likely. In CM, all
positions are equally likely for the
particle in the box.
There are positions where the
particle has zero probability to be
found.
Probability and Normalization
Although we dont know exactly where the particle might be inside the box,
we know that it has to be in the box. This means that,
2
( ) 1 x dx
=
}
2 2 2
0
sin 1
2
L
n L
C x dx C
L
t
| |
= =
|
\ .
}
(normalization condition)
So, the normalization condition fixes the final free constant C in the
wavefunction, . This then gives, 2 C L =
2
( ) sin
n
n x
x
L L
t
= (particle in a box)
Time Dependence
Note that with (x) found, we can write down the full wavefunction for the
time-dependent Schrodinger equation as:
/
( , ) ( )
iEt
n n
x t x e + =

Note that the absolute value for is unity, i.e.,
/
2
( , ) sin
iEt
n
n x
x t e
L L
t
| |
+ =
|
\ .

/ iEt
e

2
/ / / 0
1
iEt iEt iEt
e e e e
= = =

so that |+
n
(x,t)|
2
=| (x)|
2
is independent of time and probability density in
finding the particle in the box is also independent of time.
recall E hf e = =

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Ch40 Young Freedmanx

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Chapter 40/41: Quantum Mechanics

Wave Functions & 1D

(general 1D Schrdinger equation)

is a solution of the 1D Schrodingers Equation,

In fact, in general, we have,

(time dependence can

The time-independent Schrodinger equation is:

Wavefunctions for a Particle in a Box

Wavefunctions for a Particle in a Box

Note: the lowest energy

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