4

4.1

Schr
odinger Equation
Dynamics of Schr
odingers -function

Schrodinger wrote down guess for wave equation for a particle in external
potential based on de Broglies wave idea. Noted that free particle was
represented by lin. comb. of plane waves
ei(krt),

h
= h
2k 2/2m

(1)

Any lin. comb. of this type satisfies diff. eqn. with linear time
deriviative:
h2 2
=

(2)
ih
t
2m
de Broglie said the particles energy E is h
, therefore
ih

=h
= E =
t
h2 2
= E
2m

(3)
(4)

LHS of (4) looks a little like the Hamiltonian of the free particle, p2/2m
in classical physics, if we were to write
p i = H = E

(5)

Now what if particle moves in potential V (r)? S. guessed

h2 2
H = (
+ V (r)) = E
2m
1

(6)

and if the particle is not in a state of definite energy E S. guessed the

most general equation would in fact be
? ? ? ih
t = H,

H=

h2 2
2m

+ V (r)

? ??

(7)

This eqn. is the basis for much of this course. Importance: although a
guess, it systematized quantum theory, which until then was based on a
grabbag of unrelated guesses, or quantization recipes for different situations.
4.2

Hydrogen atom

Take proton to be fixed classical pt. charge, so potential e feels is

V (r) = e2/40r,

(8)

and wave eqn. for electron wave fctn. is

h2 2
+ V (r) = E,
(9)
2m
assuming the electron to be in a definite energy state w/ energy E. Assume
2
soln. dependent only on r = x + y 2 + z 2, spherically symmetric. Well
need following quantities:

= i + j + k ,
x
y
z
2
2
2
2
= 2 + 2 + 2,
x
y
z
d r x d
=
=
,
x
dr x r dr
2 x2 d2 1 d x2 d
= 2 2 +
3 ,
x2
r dr
r dr
r dr
2

(10)
(11)
(12)
(13)

d2 2 d
= 2 +
dr
r dr
2

so

(14)

and Ss eqn. becomes

d2 2 d 2m
e2
+
= 2 (E
)
dr2 r dr
40r
h

(15)

where E = E is binding energy (expect E < 0!).

Now use std. trick to solve eqns. of this type. Put = f (r)er , find
2 0 2
2mE
2e2m f
f 2f + f + f f = 2 f
r
r
h

40h
2 r
00

(16)

Choose 2 = 2mE/
h2 to get rid of 2 underlined terms
2 0 2
2e2m f
f 2f + f f =
r
r
40h
2 r
00

(17)

Now expand f in power series

f=

X
p=0

Ap[p(p1)r

p2

2pr

p1

+2pr

Aprp,

p2

2r

(18)

p1

2me2 p1
r ] = 0 (19)
+
40h
2

Since r is arbitrary, coeff. of rp1 has to vanish! This gives recursion

relation
2me2
Ap+1((p + 1)p + 2(p + 1)) = Ap(2(p + 1)
40h
2
3

(20)

or

Ap+1 2(p + 1) 2me2/(40h

2)
=
Ap
p2 + 3p + 2

(21)

Suppose the sequence doesnt terminate, i.e. numerator doesnt vanish for
any integer p 0, then as p this becomes
Ap+1
2
(2)p
= Ap

Ap
p
p!

(22)

f e2r = er f er ,

(23)

or

major bad news since would diverge at .

So instead suppose numerator vanishes for some p n 1:
me2 1
=
40h
2 n
v
u
u 2mE
u
= t 2
h

(24)
(25)

Or, lo and behold,

En =

m
2h2 n2

e2
40

(26)

agrees with Bohrs result and spectroscopy. Great success! Recall we

assumed = (r) only. Turns out there are anisotropic solns as well,
(r, , ), but they dont add any new En. Will revisit.
4.3

1D Simple Harmonic Oscillator

Classically, H = p2/2m + kx2/2. So according to S.s prescription, in

quantum version should write
h
2 2 1 2
H =
+ kx = E
(27)
2m x2 2
4

From here on out as usual there is nothing mysterious, only cookbook

techniques to solve differential equations. Well use ladder operator technique, because it allows us to discuss quantum states in somewhat intuitive
way. Define operators
v
u
u
u
t

k
h

x
2
2m x
v
u
uk
h

u
L t x +
2
2m x

L+

(28)
(29)

and note that product is

2

v
u
u
u
t

h

h
k

k
+
(x

x)
L+ L = x2
2
2m x2 2 m x x

(30)

WARNING: recall this is a differential operator. So when I write x

x
it does not mean 1, but rather is defined such that when applied to a
function (x) you get

x=
(x) = + x
x
x
x
Using this rule, easy to see that for any fctn.
5

(31)

x x = ,
x
x

(32)

or,

xx )=1
x
x
which we sometimes write in even more compact notation
(

, x] = 1
x

(33)

(34)

[A, B] = AB BA is called the commutator of two differential operators

(or noncommuting matrices!)

Now using [ x
, x] = 1 in Eq. (30), the product becomes
2

L+L =

v
u
u
u
t

k 2 h

h
k
x

2m x2} |2 {zm}
|2
{z
h

H
2

(35)

where is classical oscillation freq.

L+L = H h
/2

(36)

Similar calc. gives (check!)

L L+ = H + h
/2

(37)

[L+, L] =
h

(38)

so we have shown

Now compute commutator of L+ and H:

6

[L+, H] = [L+, L+L + h

/2]
= [L+, L+L] + [L
/2]}
+, h
|
{z
=0
= L+L+L L+LL+
= L+[L+, L]
= hL+

(39)

and similarly
[L, H] = h
L

(40)

We can now use this algebra of Ls to find the allowed energies E. Suppose
E is a solution (eigenvalue) corresponding to a solution to S.s eqn.
Operate on both sides of eqn. by L+:
L+H = L+E
([L
+{z, H]} +HL+ ) = EL+
|

(41)

h
L+
or
H(L+) = (E + h
)(L+)

(42)

So L+ is an eigenfunction (i.e. solution) with eigenvalue E + h

. L+
is called a ladder operator or raising operator, because it lifts to a
new 0 one quantum of energy h
up the ladder of energies. Check that
L is lowering operator, i.e. it gives new wavefunction with eigenvalue
reduced by h
.
? ? ? Note E cant be lowered indefinitely, at least we suspect so since
in classical physics energy is positive definite, p2/2m + kx2/2 0. For
the moment, assume E 0 and ask how the sequence of lowerings might
be terminated. Ladder of lowerings stops if we ever get
7

L0 = 0

(43)

for some 0. But we figure out the energy corresponding to 0 by expressing H as in Eq. (36):
H0 = (L
h/2)0
+ L +
| {z }
0 since L0 = 0
h

=
0.
2

(44)

So the putative lowest energy state has energy E0 h

/2. Now apply
raising operator n times:
H(L+)n0 = (E0 + n
h)(L+)n0

(45)

So we get just the spacing of levels Planck assumed, with the one minor
change that there is a it zero-point energy) h
/2 by which they are all
offset:
En = h
(n + 1/2)

(46)

Q: why doesnt zero-pt. energy affect specific heat calculation?

A: depends only on the density of levels, at least in a large system!
4.3.1

1D SHO eigenfunctions

Now lets look at the eigenfunctions of the SHO. Weve constructed a

ladder, so lets start at the bottom. The argument was that if I take, e.g.
the lowering operator L and apply it to an eigenstate n (eigenvalue En),
I will get another eigenstate corresponding to En1. Well this cant go on
forever. Physically we expect that the spectrum of En must be bounded
below, by zero certainly, since the classical Hamiltonian is positive definite!
So the only possibility to cut off the sequence of lowerings is if for some
8

eigenfunction we find that L = 0. This must be the lowest energy

eigenfunction, the so called ground state eigenfunction of the SHO, so
well start indexing from here and call the wave function 0. To find its
form we must solve the differential equation
v
u
u
u
t

k
h

(x) = 0.
x+
0
2
2m x

(47)

Now lets guess the solution. You might look for a wave function which
is centered around the origin x = 0, and which falls off rapidly very far
from 0 because there is very little chance of finding the particle there if
it has very low energy (classically, very small amplitude!). You might
guess 0 e|x|, for example, an exponential decay in both positive
and negative directions. However if you subsitute (e.g. positive x) you
find the first term gives you xex and the second one ex, except for
some constant factors. So the two terms cant cancel for all x, & this just
2
isnt a solution. How about a Gaussian, ex ?
This works, as you can
h). Check the
verify by direct substitution, if you choose = mk/(2

dimensions is an inverse length, so this rdefines a characteristic length

in the problem, 1/2 = (h2/(mk))1/4 = h
/(m), which is a kind of
quantum mechancical amplitude of oscillation in the ground state, as
we will see in the problem set.
2

Note any function Aex satisfies the lowering condition. We will want
to normalize the wave functions such that
Z

dx||2 = 1,

(48)

so plugging this in and using

Z

2y 2

v
u
u
t

,
2

(49)

which gives A = (m/(

h))1/4.
Finally, we know that we can get all the other eigenfunctions in the
ladder now by applying L+ one function at a time, starting with 1
9

L+0, etc. Note that I used instead of =, since in each case we should
apply the normalization condition. In general the solution to the SHO
differential equation is proportional to
2

n(x) = Hn(x)ex ,
where Hn is a Hermite polynomial. See Griffiths p. 56.

10

(50)