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Particles in 3D Potentials

and the Hydrogen Atom


0 2 4
0
0.5
1
1
0
g( ) x
4 0 x
P(r)
0
4a
0

0
1
r
r = a
0

z
x
L
L
L
( )
2 2 2
2
2
8
z y x n n n
n n n
mL
h
E
z y x
+ + =
) ( ) ( ) ( ) , , ( z y x z y x =
o
a / r
3
o
e
a
1
) r (

=
t

2
6 13
n
eV .
E
n

=
Overview

3-Dimensional Potential Well
Product Wavefunctions
Concept of degeneracy
Early (Incorrect!) Models of the Hydrogen Atom
Planetary Model
Schrdingers Equation for the Hydrogen Atom
Semi-quantitative picture from uncertainty principle
Ground state solution*
Spherically-symmetric excited states (s-states)*
*contain details beyond what we expect you to learn here
Quantum Particles in 3D Potentials
One consequence of confining a quantum particle in two or
three dimensions is degeneracy -- the occurrence of
several quantum states at the same energy level.



So far, we have considered quantum particles
bound in one-dimensional potentials. This
situation can be applicable to certain physical
systems but it lacks some of the features of
many real 3D quantum systems, such as
atoms and artificial quantum structures:
(www.kfa-juelich.de/isi/)
A real (3D)
quantum dot
To illustrate this important point in a simple system, we
extend our favorite potential -- the infinite square well --
to three dimensions.


Particle in a 3D Box (1)
outside box, x or y or z < 0
outside box, x or y or z > L
0 inside box U(x,y,z) =
Lets solve this SEQ for the particle in a 3D box:
y
The extension of the Schrdinger Equation (SEQ) to 3D
is straightforward in cartesian (x,y,z) coordinates:



E ) z , y , x ( U
dz
d
dy
d
dx
d
m
= +
|
|
.
|

\
|
+ +
2
2
2
2
2
2 2
2

) , , ( z y x
where
This simple U(x,y,z) can be separated
A special feature
U(x,y,z) = U(x) + U(y) + U(z)
z
x
L
L
L
Kinetic energy term in the
Schrdinger Equation
( )
2 2 2
2
1
z y x
p p p
m
like + +
Easy to see in this case since U = 0 or
Very useful in general as illustrated
in the solution on the following slide
Particle in a 3D Box (2)
So, the whole problem simplifies into three one-dimensional
equations that weve already solved in Lecture 7.
) ( ) ( ) (
) (
2
2
2 2
x E x x U
dx
x d
m
x

= +

) ( ) ( ) (
) (
2
2
2 2
y E y y U
dy
y d
m
y

= +

|
.
|

\
|
= x
L
n
N x
x
n
t
sin ) (
2
2
2 2
|
.
|

\
|
=
L
n
m
h
E
x
nx
|
|
.
|

\
|
= y
L
n
N y
y
n
t
sin ) (
2
2
2 2
|
|
.
|

\
|
=
L
n
m
h
E
y
ny
..Likewise for (z)..
So the Schrdinger Equation becomes:

( )

E ) z ( U ) y ( U ) x ( U
dz
d
dy
d
dx
d
m
= + + +
|
|
.
|

\
|
+ +
2
2
2
2
2
2 2
2

and the wavefunction can be separated


into the product of three functions:
) , , ( z y x
) ( ) ( ) ( ) , , ( z y x z y x =
graphic
Note that the functions | can
be different for x, y, and z
Particle in a 3D Box (3)
So, finally, the eigenstates and associated
energies for a particle in a 3D box are:

z
x
y
L
L
L
|
.
|

\
|
|
|
.
|

\
|
|
.
|

\
|
= z
L
n
y
L
n
x
L
n
N
z
y
x
t
t
t
sin sin sin
where n
x
,n
y
, and n
z
can each have values 1,2,3,.
This problem illustrates 2 important new points.
(1) Three quantum numbers (n
x
,n
y
,n
z
) are needed to completely
identify the state of this three-dimensional system.
(2) More than one state can have the same energy:
Degeneracy.
Degeneracy reflects an underlying symmetry in U(x,y,z)
3 equivalent directions
( )
2 2 2
2
2
8
z y x n n n
n n n
mL
h
E
z y x
+ + =
Consider a particle in a two-dimensional (infinite) well, with L
x
= L
y
.
1. Compare the energies of the (2,2), (1,3), and (3,1) states?
a. E
(2,2)
> E
(1,3)
= E
(3,1)

b. E
(2,2)
= E
(1,3)
= E
(3,1)

c. E
(1,3)
= E
(3,1)
> E
(2,2)


2. If we squeeze the box in the x-direction (i.e., L
x
< L
y
) compare
E
(1,3)
with E
(3,1)
:
a. E
(1,3)
< E
(3,1)

b. E
(1,3)
= E
(3,1)

c. E
(1,3)
> E
(3,1)

Lecture 11, Act 1
Consider a particle in a two-dimensional (infinite) well, with L
x
= L
y
.
1. Compare the energies of the (2,2), (1,3), and (3,1) states?
a. E
(2,2)
> E
(1,3)
= E
(3,1)

b. E
(2,2)
= E
(1,3)
= E
(3,1)

c. E
(1,3)
= E
(3,1)
> E
(2,2)


2. If we squeeze the box in the x-direction (i.e., L
x
< L
y
) compare
E
(1,3)
with E
(3,1)
:
a. E
(1,3)
< E
(3,1)

b. E
(1,3)
= E
(3,1)

c. E
(1,3)
> E
(3,1)

Lecture 11, Act 1 - Solution
E
(1,3)
= E
(1,3)
= E
0
(1
2
+ 3
2
) = 10 E
0

The tighter confinement along x will increase
the contribution to E. The effect will be
greatest on states with greatest n
x
:
E
(2,2)
= E
0
(2
2
+ 2
2
) = 8 E
0

( )
2
2 2
( ) (1,3) (3,1)
2
4 4 9; 36 1
8
x y
n n x y
y
h
E n n E E
mL
= + + +
Example: L
x
= L
y
/2
2
2 2
2 2
8
x y
y
x
n n
x y
n
n h
E
m L L
| |
= +
|
|
\ .
z
x
y
L
L
L
D=1
6E
o

(2,1,1) (1,2,1) (1,1,2)
D=3
(1,1,1)
3E
o

(n
x
,n
y
n
z
)
( )
2
z
2
y
2
x
2
2
n n n
n n n
mL 8
h
E
z y x
+ + =
n
x
,n
y
,n
z
= 1,2,3,...
Energy levels (1)
Now back to a 3D cubic box:
Show energies and label (n
x
,n
y
,n
z
) for the first
11 states of the particle in the 3D box, and
write the degeneracy D for each allowed energy.
Use E
o
= h
2
/8mL
2
.
E
z
x
y
L
L
L
D=1
6E
o

(2,1,1) (1,2,1) (1,1,2)
D=3
(1,1,1)
3E
o

(n
x
,n
y
n
z
)
( )
2
z
2
y
2
x
2
2
n n n
n n n
mL 8
h
E
z y x
+ + =
n
x
,n
y
,n
z
= 1,2,3,...
Energy levels (1)
Now back to a 3D cubic box:
Show energies and label (n
x
,n
y
,n
z
) for the first
11 states of the particle in the 3D box, and
write the degeneracy D for each allowed energy.
Use E
o
= h
2
/8mL
2
.
E
9E
o

11E
o

12E
o

For a symmetric cube infinite box, we just saw that the 5
th
energy
state has an energy of 12 E
0
and a degeneracy of 1, with quantum
numbers (2,2,2).
1. What is the energy of the next energy level?
a. 13E
0

b. 14E
0

c. 15E
0


2. What is the degeneracy of this energy level?
a. 2
b. 4
c. 6

Lecture 11, Act 2
For a symmetric cube infinite box, we just saw that the 5
th
energy
state has an energy of 12 E
0
and a degeneracy of 1, with quantum
numbers (2,2,2).
1. What is the energy of the next energy level?
a. 13E
0

b. 14E
0

c. 15E
0


2. What is the degeneracy of this energy level?
a. 2
b. 4
c. 6

Lecture 11, Act 2 - Solution
E
(1,2,3)
= E
0
(1
2
+ 2
2
+ 3
2
) = 14 E
0
Any ordering of the quantum numbers
1, 2, and 3 will give the same total
energy. There are 6 possible ways to
order them: (1,2,3), (1,3,2), (2,1,3),
(3,1,2), (2,3,1), (3,2,1).

Note: For this system, 6 is the
maximum possible degeneracy.

E
3E
o

6E
o

9E
o

11E
o

(n
x
,n
y
,n
z
)
z
x
y
L
1

L
2
> L
1

L
1

Energy levels (2)
Now consider a non-cubic box:
Assume that the box is stretched only along
the y-direction. What do you think will
happen to the cubes energy levels below?
( ) ( )
2
y
2
2
2
2
z
2
x
2
1
2
n n n
n
mL 8
h
n n
mL 8
h
E
z y x
+ + =
(1) The symmetry of U is
broken for y, so the three-
fold degeneracy is lowereda
two-fold degeneracy remains
due to 2 remaining equivalent
directions, x and z.
(1,1,1)
D=1
(1,2,1)
D=1
D=2
(2,1,1) (1,1,2)
(2) There is an overall lowering
of energies due to decreased
confinement along y.
E
3E
o

6E
o

9E
o

11E
o

(n
x
,n
y
,n
z
)
Energy levels (2)
Now consider a non-cubic box:
Assume that the box is stretched only along
the y-direction. What do you think will
happen to the cubes energy levels below?
z
x
y
L
1

L
2
> L
1

L
1

( ) ( )
2
y
2
2
2
2
z
2
x
2
1
2
n n n
n
mL 8
h
n n
mL 8
h
E
z y x
+ + =
Figure out
next level.
Another 3D System: The Atom
-electrons confined in Coulomb field of a nucleus
Geiger-Marsden (Rutherford) Experiment (1911):
Measured angular dependence of o particles
(He ions) scattered from gold foil.
Mostly scattering at small angles
supported the plum pudding model. But
Occasional scatterings at large angles Something massive in there!
u
Au
o
v
a nucleus!
Discrete Emission and Absorption spectra
When excited in an electrical discharge, atoms
emitted radiation only at discrete wavelengths
Different emission spectra for different atoms

Early hints of the quantum nature of atoms:
(nm)
Atomic hydrogen

Conclusion: Most of atomic mass is
concentrated in a small region of the atom
Rutherford Experiment


Atoms: Classical Planetary Model

Classical picture: negatively charged objects
(electrons) orbit positively charged nucleus
due to Coulomb force.
There is a BIG PROBLEM with this:
As the electron moves in its circular orbit,
it is ACCELERATING.
As you learned in Physics 212, accelerating
charges radiate electromagnetic energy.
Consequently, an electron would
continuously lose energy and spiral into the
nucleus in about 10
-9
sec.
+Ze
-e
F
(An early model of the atom)
The planetary model doesnt lead to stable atoms.




How do we describe the hydrogen
atom quantum mechanically?
We need to specify U, the potential
energy of the electron:
We assume that the Coulomb force
between the electron and the nucleus
is the force responsible for binding
the electron in the atom
This spherically symmetric problem can be solved in
spherical coordinates.
Potential Energy for the Hydrogen Atom
We cannot separate this potential energy in xyz coordinates
as we did for the 3D box, U(x,y,z) = U(x) + U(y) + U(z)
,
which led to the product wavefunctions: (x,y,z) = |(x) |(y) |(z)
r
e
) r ( U
2
k
=
r
U(r)
0
2 2 9
0
C / Nm 10 9
4
1
= =
tc
k
But first: Hydrogen atom qualitatively
Why doesnt the quantum electron collapse into the
nucleus, where its potential energy is lowest?
The more confined it gets, the bigger p spread it has, from
Heisenberg Uncertainty. More p
2
/2m means more KE.
So theres a tradeoff between lowering PE and raising KE.
About what spread a
0
minimizes KE+PE?
Roughly,


Take derivative,
find a
0
to
minimize E:
2 2 2
2
0
2 2
o
p e
E KE PE PE
m ma a
k
= + = + ~ +
2 2 4
2 2
2 4
2
so 2
so
2
o
m e
a PE KE
m e
m e
E
k
k
k

~ ~ =

~
virial theorem
Exact, generally
true for atoms
Doing the same thing carefully ends up
with the same result!
So the general energy and size scale
of an atom are fixed by
the Heisenberg Uncertainty relation.
Consider an electron around a nucleus that has two protons
(and two neutrons, like an ionized Helium atom).
1. Compare the effective Bohr radius a
0,He
with the usual Bohr
radius for hydrogen, a
0
:
a. a
0,He
> a
0

b. a
0,He
= a
0

c. a
0,He
< a
0


2. What is the ratio of ground state energies E
0,He
/E
0,H
?
a. E
0,He
/E
0,H
= 1
b. E
0,He
/E
0,H
= 2
c. E
0,He
/E
0,H
= 4
Lecture 11, Act 3
Consider an electron around a nucleus that has two protons
(and two neutrons, like an ionized Helium atom).
1. Compare the effective Bohr radius a
0,He
with the usual Bohr radius
for hydrogen, a
0
:
a. a
0,He
> a
0

b. a
0,He
= a
0

c. a
0,He
< a
0


2. What is the ratio of ground state energies E
0,He
/E
0,H
?
a. E
0,He
/E
0,H
= 1
b. E
0,He
/E
0,H
= 2
c. E
0,He
/E
0,H
= 4
Lecture 11, Act 3 - Solution
Look at how a
0
depends on the charge:
Clearly the electron will be more tightly bound, so
|E
0,He
| > |E
0,H
| . How much more tightly?
Look at E
0
:
In general, for a hydrogenic
atom with Z protons:
2 2
0
0 0,
2
(2 ) 2
He
a
a a
m e m e e k k
=
This makes sense more charge
stronger attraction electron sits
closer to the nucleus
2
0, 0, 0,
(2 )
4
2 2( / 2)
H He H
o o
e e e
E E E
a a
k k
= = =
2
0, 2
,
2 2
13.6
H
n Z
E
Z
E Z eV
n n
= =
Depends
on
which
state
Product Wavefunction in Spherical Coordinates
The potential is spherically symmetric, i.e., U(r )
depends only on the radius. Therefore the
problem is separable and the solution to the SEQ
in spherical coordinates is a product wave
function of the form:

x
y
z
r
u
|
) r ( R E ) r ( R
r
e
r
r
r
1
m 2
0 n n 0 n
2
2
2 2
=
|
|
.
|

\
|

c
c k
KE term PE term
) r ( R ) , , r (
0 n
= | u
s-state
Wavefunction:
) , ( ) ( ) , , ( | u | u
lm nl nlm
Y r R r = +
with quantum numbers: n l and m
principal orbital magnetic
(angular momentum)
Here R
nl
is the radial part, and Y
lm
are spherical harmonics. The
Schrdinger equation in spherical coordinates is complicated. An
appreciation of the problem can be gained by considering only spherically
symmetric states (wavefunctions with no angular dependence). For these
s-states, l = 0 and m = 0, and the radial SEQ takes the form:
Radial Eigenstates of H:
s-state wavefunctions
The zeros in the subscripts below are a reminder that these are
states with zero angular momentum.
The radial eigenstates, R
no
(r) , for the electron in the
Coulomb potential of the proton are plotted below:
0
3 /
2
0 0
0 , 3
3
2
2
3 ) (
a r
e
a
r
a
r
r R

|
|
.
|

\
|
|
|
.
|

\
|
+ 0
2 /
0
0 , 2
2
1 ) (
a r
e
a
r
r R

|
|
.
|

\
|

0
/
0 , 1
) (
a r
e r R

r
R
30

0 5 10 15
0
2
3
.5
d4( ) x
15 0 x
r
15a
0

0
0
r
R
20

0 5 10
0
0.5
1
1
.2
h( ) x
10 0 x
10a
0

0
0
0 2 4
0
0.5
1
1
0
f( ) x
4 0 x
R
10

0
0
4a
0

2 2
o
2
n
n
eV 6 . 13
n
1
a 2
e
E

=

=
k 2
2
0
e m
a
k

= Bohr radius = 0.053 nm


Plug these into radial SEQ (Appendix)
Probability Density of Electrons
Probability density = Probability per unit volume = ,,
2
R
n0
2
for s-states.
The density of dots plotted below is proportional to R
n0
2
.
r
0 2 4
0
0.5
1
1
0
f( ) x
4 0 x
R
10

0
0
4a
0

r
R
20

0 5 10
0
0.5
1
1
.2
h( ) x
10 0 x
10a
0

0
0
1s state
2s state
Radial Probability Densities for s-states
Summary of wave functions and radial probability
densities for some s-states:
r
R
20

0 5 10
0
0.5
1
1
.2
h( ) x
10 0 x
0
10a
0

0
0 5 10
0
0.2
0.4
.5
0
h2( ) x
10 0 x
0
10a
0

0
r
P
20

0 2 4
0
0.5
1
1
0
g( ) x
4 0 x
P
10

0
4a
0

0
r
0 2 4
0
0.5
1
1
0
f( ) x
4 0 x r
0
4a
0

0
R
10

radial wave functions radial probability densities, P(r)
R
30

0 5 10 15
0
2
3
.5
d4( ) x
15 0 x r
0
15a
0

0
0 20a
0
r
P
30

These P(r) include both |
2
(r)| and a factor of r
2
because bigger r shells have more volume.
Optical Transitions in H -- Example
An electron, initially excited to the n = 3
energy level of the hydrogen atom, falls
to the n = 2 level, emitting a photon in
the process. What are the energy and
wavelength of the photon emitted?
-15
-10
-5
0
0 5 10 15 20
r/a
0

E (eV)
U(r)
-15
0
0 20
E
2

E
1

E
3

Answer:
(nm)
Atomic hydrogen
Discharge tubes
-15
-10
-5
0
0 5 10 15 20
r/a
0

E (eV)
U(r)
-15
0
0 20
E
2

E
1

E
3

2
13.6 eV
n
E
n

=
2 2
1 1
13.6 eV
i f
n n
i f
E
n n

| |
A =
|
|
\ .
Therefore:
3 2
1 1
13.6 eV 1.9eV
9 4
photon
E E

| |
= A = =
|
\ .
1240eV nm
656nm
1.9eV
photon
hc
E


= = = (nm)
Atomic hydrogen
Optical Transitions in H --Example
An electron, initially excited to the n = 3
energy level of the hydrogen atom, falls
to the n = 2 level, emitting a photon in
the process. What are the energy and
wavelength of the photon emitted?
You will experimentally measure several transitions in Lab.
The Radial Equation
( )
2
2
2
2 2
2 2 2
0 0
1
1
0
2 2 1
, , , 1,2,3,
2
n
n n
l l
dR a
d
r b R
dr r r dr r
mE Z Z
a b E n
a ma n
+ (
| |
+ + + =
(
|
\ .

= = =
( )
( ) ( )
2
2
2
00
sin sin 1 sin 0
, ,
0,1, 2, , 1 , 1, , 1,
0 0; Constant
lm
Y
Y
l l Y
Y Y
l n m l l l l
l m Y
u u u
u
u
u u
c
| | c c
+ + + =
|
c
c c
\ .

= = +
= = =
The Angular Equation
( ) ( )
( )
( )
( )
3/ 2
0
0
0 0
1
2 1
1
, , ,
2
1
,
!
nlm nl lm
Z
r
na
l
nl nl nl n
n l
n l x
l x
nl
n l
r R Y
Z Z
R r C r e L r C
na na
n
d
L x x e x e
dx
u u
t


+


+ =
| | | |
= =
| |
\ . \ .
=
The Wave Function