Review: Particle in rigid 3D box

Today:
Rest of the 3D rigid box
The Hydrogen atom

h2 2 2 2

( x, y, z) + V ( x, y, z) ( x, y, z) = E ( x, y, z)
+
+
2m x2 y 2 z 2
V(x,y,z) = 0 inside; outside.

Final Exam is on Wednesday, Dec. 14,

1:30pm-4pm in G1B20 (our classroom).
Allowed materials: One letter paper-sized,
handwritten cheat-sheet and a calculator. (No
cell-phones, PCs, textbooks, BBQs etc.)

Separation of variables approach:

(x,y,z) = X(x)Y(y)Z(z)
Solutions:

c
a

2h2

k = n , Ex = n2
, n = 1,2,3....
a
2ma 2

X ( x) = A sinkx x ,

and similar for Y(y) and Z(z).

Exam format: Similar to Exam 1- 3 (all

bubble; emphasis on understanding
concepts)

2D box: Square of the wave function for nx=ny=1

And the total energy is:

E = E x + E y + Ez

Or for a cube (a=b=c):

E = E0 (n x2 + n 2y + nz2 ) , E0 =

100%

0%

ny

nx

Sometimes, there are several solutions with the exact

same energy. Such solutions are called degenerate.

2ma 2

2D box: Square of the wave function of selected

excited states

Percent relative
to maximum

Degeneracy

2h 2

Q1:

The ground state energy of the 2D box of size L x L is 2E0, where

E0 = 22/(2mL2) is the ground state energy of a 1D box of size L.
y

E=E0(nx2+ny2)
E=

E0(nx2+ny2+nz2)
L

What is the energy of the 1st excited state of this 2D box?

a)3E0
b)4E0
c) 5E0
d)8E0
Degeneracy of 1 means non-degenerate

Q2:

Imagine a 3D cubic box of sides L x L x L. What is

the degeneracy of the ground state and the first
excited state?
E = E (n 2 + n 2 + n 2 )
0

Why? Scattering showed hard core.

Problem: electrons should spiral into nucleus in ~10-11 sec.

Bohr fixed energy levels

1, 1
3, 1
1, 3
3, 3
0, 3

Why? Known that negative charges can be removed from atom.

Problem: Rutherford showed nucleus is hard core.

Rutherford Solar System

Degeneracy of ground state

Degeneracy of 1st excited state
a)
b)
c)
d)
e)

Review Models of the Atom

Thomson Plum Pudding

Why? Fits to spectral lines of Hydrogen

Problem: No reason for fixed energy levels
Structure doesnt fit physics

deBroglie electron standing waves

Why? Explains fixed energy levels

Problem: still only works for Hydrogen.

Schrodinger quantum wave functions

Why? Explains everything!
Problem: None (except that its hard to understand)

What is Schrodingers model of

the hydrogen atom?

Schrodingers Solutions for Hydrogen

If you understand the 1D quantum well (and how we
went from 1D to 3D), then it is easy for you to
understand Schrdinger's hydrogen atom!

Electron is cloud of probability whose wave

function (x,y,z,t) is the solution to the
Schrodinger equation:

h2 2 2 2

( x, y, z, t )
+
+
2m x2 y 2 z 2

+ V ( x, y, z)( x, y, z, t ) = ih ( x, y, z, t )
t
# of protons in nucleus
Coulomb constant

where:

V ( x, y , z ) =

All thats really different is the potential V(r) 1/r

(Coulomb)

Zke
Zke
= 2
r
( x + y 2 + z 2 )1/ 2

OK. Mathematically it is a bit involved, For now,

focus on the concept and let someone else do the
math for you!

(Coulomb potential; no time dependence)

Can get rid of time dependence and simplify:

Equation in 3D, looking for (x,y,z,t):

h2 2 2 2

( x, y, z, t)
+
+
2m x2 y 2 z 2

+ V ( x, y, z)( x, y, z, t ) = ih ( x, y, z, t)
t

Quick note on vector derivatives

Laplacian (or Laplace operator) in cartesian coordinates:

2 2 2
+
+
x 2 y 2 z 2

Same thing! Just different coordinates.

Since V(x,y,z) not function of time:

( x, y, z , t ) = ( x, y, z )e iEt / h

Laplacian in spherical coordinates:

E ( x, y, z )e iEt / h

Time independent Schrodinger Equation (analogous to 1D):

h2 2 2 2
2 + 2 + 2 ( x, y, z) + V ( x, y, z) ( x, y, z) = E ( x, y, z)
2m x y z

2 =

1 2
1
1
2
r
+ 2
sin
+ 2 2
2
r r r r sin
r sin 2

3D Schrdinger with Laplacian (coordinate free):

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

Since potential is spherically

symmetric ( V ( r ) = Zke 2 / r ),
easier to solve w/ spherical coords:

Q3:

z
Watch out:
Physicists
convention!

Time-independent Schrodinger
eqn. in spherical coordinates:

V(r)

In 1D (electron in a wire):
we got quantization from applying
boundary conditions in terms of x.

h 2 1 2

r
2m r 2 r r

1


1
2
sin
+
+V ( r ) = E

r 2 sin 2 2
r 2 sin

x
(x,y,z) =
(rsincos, rsinsin, rcos)

Technique for solving: Separation of Variables

In 3D: have 3 degrees of freedom.

Boundary conditions in terms of r,,
What are the boundary conditions on the wave function in r ?
A. must go to 0 at r=0
B. must go to 0 at r=infinity
C. at r=infinity must equal to at r=0, but value can be non-zero.
D. A and B
E. A, B, and C

(similar to particle in a 3D box, but now in spherical coordinates)

(r , , ) = R(r ) f ( ) g ( )
(r , , , t ) = R (r ) f ( ) g ( ) e iEt / h

Q4:

r
x

nlm (r , , ) = Rnl (r ) f lm ( ) g m ( )
Shape of depends on n, l ,m. Each (n,l,m) gives unique
n=1, 2, 3 = Principle Quantum Number

2p

a. 1
b. 3
c. 4
d. 6
e. 9

l=0, 1, 2, 3 = Angular Momentum Quantum Number

(restricted to 0, 1, 2 n-1)

=s, p, d, f

n=2
m = ... -1, 0, 1.. = z-component of Angular Momentum
l=1
(restricted to l to l)
m= -1,0,1

The Hydrogen atom

3D-Schrdinger with V(r) = -ke2/r
h2 2
ke 2
( r, , )
( r, , ) = E ( r, , )
2m
r

2
with: =

In 3D, now have 3 degrees of freedom:

Boundary conditions in terms of r,,
Have 3 quantum numbers (n, l, m)

How many quantum numbers are there in 3D?

In other words, how many numbers do you need to
specify unique wave function? And why?

In 1D (electron in a wire):
Have 1 quantum number (n)

In 1D (electron in a wire):
Have 1 quantum number (n).
Need to specify value of n to know
what state electron is in.
nx iEnt / h
2
( x, t ) = ( x )e iEnt / h =
sin(
)e
L
L
In 3D, now have 3 degrees of freedom (ignore spin):
3 sets of boundary conditions in terms of r,,

1 2
1
1
2


sin
+
+

r 2 sin 2 2
r 2 r r r 2 sin

Comparing H atom & Infinite Square Well

Infinite Square Well: (1D)
V(x) = 0 if 0<x<L

otherwise

(r , , ) = R(r ) f ( ) g ( )
Once we have (r,,) we also know the time-dependent solution:

(r , , , t ) = R (r ) f ( ) g ( ) e iEt / h
Done!

Energy eigenstates:
n 2 2 h 2
En =

Use separation of variables:

H Atom: (3D)
V(r) = -ke2/r

2mL2

Wave functions:
n ( x) = L2 sin( nLx )

n ( x, t ) = n( x )e iEnt / h

Energy eigenstates:

mk 2 e 4
2h 2 n 2
Wave functions:
En =

nlm (r , , ) = Rnl (r ) f lm ( ) g m ( )
nlm (r , , , t ) = nlm (r , , )e iEnt / h
: generalized Laguerre polynomials
: spherical harmonic functions

Answers to clicker questions

Q1: C; nx=1, ny=2 or nx=2 ny=1s
Q2: C
Ground state = 1,1,1 : E1 = 3E0
1st excited state: 2,1,1 1,2,1 1,1,2 : all same E2 = 6 E0
Q3: B

must be normalizable, so needs to go to zero at r

(Also makes sense physically: not probable to find electron there)
NOTE: (0)=const. is sufficient! Probability of finding it around r~0 is proportional to: 4r2||2.

Q4: B