3D Schrodinger Equation

Simply substitute momentum operator

do particle in box and H atom
added dimensions give more quantum numbers. Can have degeneracies (more than 1 state with same energy).
Added complexity.

p i

Solve by separating
variables
2
2m

or

2
x 2

2 ( x, y , z, t ) V ( x, y , z, t )

i
t

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

2 V ( x, y , z ) E
P460 - 3D S.E.

 If V well-behaved can separate further: V(r) or Vx(x)+Vy(y)+Vz(z).

Looking at second one:
2
2m

2 (Vx ( x ) V y ( y ) Vz ( z )) E

assume ( x , y , z )
2
2m

2
2m

( x )

( x 2

2
y 2

) (Vx V y )

( x 2

2
y 2

) x

x y z

( y )

2
2m

(Vx V y )

( z)

2
z 2

2
2m

LHS depends on x,y

( E Vz )

x y z

2 z
E Vz
z z 2

RHS depends on z

2 d 2 z

( E Vz ) S
z dz 2
2m
2
1
2
2
(

) x y Vx V y S
x y
x 2
y 2
2m

S = separation constant. Repeat for x and y

P460 - 3D S.E.

2
2 d x
2 m x dx 2

Vx S ' E x

2
2 d y
2 m y dy 2

Vy S S ' E y

2
2 d z
2 m z dz 2

Vz E S E z

E x E y E z S '( S S ' ) ( E S ) E

Example: 2D (~same as 3D) particle in a Square Box

V
x 0, x a , y 0, y a
V 0
inside box
satisfies
V Vx ( x ) V y ( y )

( x , y ) x ( x ) y ( y )

solve 2 differential equations and get

E Ex E y

2 2
2 ma 2

( n x2 n y2 )

symmetry as square. broken if rectangle

P460 - 3D S.E.

E Ex E y

( x, y ) A sin

2 2
2 ma 2
n x x
a

| |2 dxdy 1

( n x2 n y2 )
sin

n y y
a

n x , n y 1,2..

normalizat ion

2D gives 2 quantum numbers.

Level
nx
ny
1-1
1
1
1-2
1
2
2-1
2
1
2-2
2
2

P460 - 3D S.E.

Energy
2E0
5E0
5E0
8E0

for degenerate levels, wave functions can mix (unless something

breaks degeneracy: external or internal B/E field, deformation.)

12 A sin

21 A sin

2x
a

sin

2y
a

sin

y
a

mix 12 21

this still satisfies S.E. with E=5E0

P460 - 3D S.E.

Spherical Coordinates
Can solve S.E. if V(r) function only of radial coordinate
2
2M

2 V ( r ) E ( r , , )

2
2M

[ r 2r ( r 2

r2

1
sin
1
sin 2

(sin

2
2

] ( r , , ) V ( r ) E

volume element is
d (vol ) dr ( rd )( r sin d )

P460 - 3D S.E.

Spherical Coordinates
solve by separation of variables

( r , , ) R ( r ) ( ) ( )
( E V ) R 2 M
2

2
r r

r2

r 2
r
1
sin 2

2
2

1
sin 2

sin

) R

multiply each side by

r 2 sin 2
R

P460 - 3D S.E.

Spherical Coordinates-Phi
Look at phi equation first. Have separation constant
1

d2
d 2

( ) f ( r , ) ml2

constant (knowing answer allows form)

must be single valued

( ) e iml

( 2 ) ( )
e iml ( 2 ) e iml ml 0,1,2.......
the theta equation will add a constraint on the m quantum number

P460 - 3D S.E.

Spherical Coordinates-Theta
Take phi equation, plug into (theta,r) and rearrange. Have second
separation constant
1
R

d
dr
ml2

sin 2

r 2 dR
dr

1
sin

[ E V ( r )]

2 M 2r2
2
d
d

( sin dd )

l ( l 1)
knowing answer gives form of constant. Gives theta equation which
depends on 2 quantum numbers.
d
1
sin d

sin d
d

ml2
2

sin

P460 - 3D S.E.

l (l 1)
9

Spherical Coordinates-Theta
d
1
sin d

sin d
d

ml2
sin 2

l (l 1)

Associated Legendre equation. Can use either analytical (calculus) or

algebraic (group theory) to solve. Do analytical. Start with Legendre
equation

(1 z )
2

d 2 Pl
dz 2

z cos

2z

dPl
dz

l (l 1) Pl 0

Pl Legendre function

P460 - 3D S.E.

10

Spherical Coordinates-Theta
Get associated Legendre functions by taking the derivative of the
Legendre function. Prove by substitution into Legendre equation
lml (1 z

|ml |/ 2

d |ml | Pl
dz |ml

20 P2
21 (1 z

22 (1 z 2 )

1
2

dPl
dz

2 1

Pl

dz 2

Note that power of P determines how many derivatives one can do.
Solve Legendre equation by series solution
(1 z
Pl
d 2P
dz 2

Pl

dz 2

a
k 0

2z

a
k 2

dPl
dz

dP
dz

l (l 1) Pl 0

a
k 1

kz k 1

k ( k 1) z k 2
P460 - 3D S.E.

11

Solving Legendre Equation

Plug series terms into Legendre equation

k 2
k
{
k
(
k

1
)
a
z

[
k
(
k

1
)

l
(
l

1
)]
a
z
} 0

k
k

let k=j+2 in first part and k=j in second (think of it as having two
independent sums). Combine all terms with same power

{( j 2)( j 1) a

j2

gives recursion relationship

[ j ( j 1) l (l 1)]a j }z

a j2

j ( j 1) l ( l 1)
( j 2 )( j 1)

aj

series ends if a value equals 0 L=j=integer

a j 2 0 j ( j 1) l (l 1)

end up with odd/even (Parity) series

a1 0, aeven 0 or a0 0, aodd 0
P460 - 3D S.E.

12

Solving Legendre Equation

Can start making Legendre polynomials. Be in ascending power order
l 0, a0 1, a1 0 P0 1
l 1, a0 0, a1 1 P1 z
l 2, a0 1, a1 0, a2

06
21

j ( j 1) l ( l 1)
( j 2 )( j 1)

3 P2 1 3 z 2

can now form associated Legendre polynomials. Can only have l

derivatives of each Legendre polynomial. Gives constraint on m (theta
solution constrains phi solution)

lml (1 z )
2

|ml |/ 2

d |ml |
dz |ml |

Pl

| ml | l
P460 - 3D S.E.

13

Spherical Harmonics

00 1

z cos

10 z
1, 1 (1 z

1
2

20 1 3 z 2
2 , 1 (1 z

1
2

2 , 2 (1 z 2 )

The product of the theta and phi terms are called Spherical
Harmonics. Also occur in E&M. See Table on page 127 in book
They hold whenever V is function of only r. Saw related to angular
momentum

Ylm lm m

spherical harmonics
P460 - 3D S.E.

14

3D Schr. Eqn.-Radial Eqn.

For V function of radius only. Look at radial equation. L comes in from
theta equation (separation constant)
1 d

r dr

r 2 dR
dr

2
V ( r ) E ) R
2

l ( l 1)

R
r2

can be rewritten as (usually much, much better...)

2 d 2u
2 l ( l 1)

(V
)u Eu
2
2
2 dr
2
r
u ( r ) rR ( r )

and then have probability

P ( r ) 4R 2 r 2 dr
4u 2 dr
P460 - 3D S.E.

15

3D Schr. Eqn.-Radial Eqn.

2 d 2u
2 l ( l 1)

(V
)u Eu
2
2
2 dr
2
r
u ( r ) rR ( r )
note L(L+1) term. Angular momentum. Acts like repulsive potential and
goes to infinity at r=0 (ala classical mechanics)
energy eigenvalues typically depend on 2 quantum numbers (n and L).
Only 1/r potentials depend only on n (and true for hydrogen atom only
in first order. After adding perturbations due to spin and relativity,
depends on n and j=L+s.

P460 - 3D S.E.

16

Particle in spherical box

u ( r ) rR ( r )

Good first model for nuclei

V (r) 0
V (r)

r a
r a

plug into radial equation. Can guess solutions

2 d 2u
2 l ( l 1)

(V
)u Eu
2 dr 2
2
r2
2 d 2u
2 l ( l 1)

u El u
2
2
2 dr
2
r

look first at l=0

d 2u
dr 2

k 2u

with

2 ME

u A sin( kr ) B cos( kr )

P460 - 3D S.E.

17

Particle in spherical box

l=0

d 2u
dr 2

k 2u

with

2 ME

u A sin( kr ) B cos( kr )

boundary conditions. R=u/r and must be finite at r=0. Gives B=0. For
continuity, must have R=u=0 at r=a. gives sin(ka)=0 and

Enlm En 00

n 00

1
2a

n 1,2....

n 2 2 2
2 Ma 2

sin( nr / a )
r

note plane wave solution. Supplement 8-B discusses scattering,

phase shifts. General terms are
ik r
R( r )

P460 - 3D S.E.

18

Particle in spherical box

ForLl>0 solutions are Bessel functions. Often arises in scattering off
spherically symmetric potentials (like nuclei..). Can guess shape
(also can guess finite well)
energy will depend on both quantum numbers
Enl E10 E11 E12 E20 E21 E22 .....

and so 1s 1p 1d 2s 2p 2d 3s 3d .and ordering (except

higher E for higher n,l) depending on details
gives what nuclei (what Z or N) have filled (sub)shells being different
than what atoms have filled electronic shells. In atoms:
Z 2
1S

in nuclei (with j subshells)

4 10 ( He Be Ne)
2S 2 P

Z 2 6 8 14 16 ( He C O Si S )
1s 1 p 3 1 p 1 1d 5 2 s 1
2

P460 - 3D S.E.

19

H Atom Radial Function

For V =a/r get (use reduced mass)
1 d r 2 dR
2m

r dr
dr
2

Ze 2
l ( l 1)

E R
R
2
4 0 r
r

Laguerre equation. Solutions are Laguerre polynomials. Solve using series

solution (after pulling out an exponential factor), get recursion relation, get
eigenvalues by having the series endn is any integer > 0 and L<n. Energy
doesnt depend on L quantum number.

En

MZ 2 e 4
( 4 0 ) 2 2 2 n 2

me c 2 2 Z 2
2n2

13.6 eVZ 2
n2

Where fine structure constant alpha = 1/137 used. Same as Bohr model energy

P460 - 3D S.E.

20

H Atom Radial Function

Energy doesnt depend on L quantum number but range of L restricted
by n quantum number.
l<n n=1 only l=0 1S
n=2
l=0,1
2S 2P
n=3
l=0,1,2
3S 3P 3D
2 2 2
2

En

me c Z
2n2

13.6 eVZ
n2

eigenfunctions depend on both n,L quantum numbers. First few:

R10 e

Zr / a0

R20 ( 2
R21

Zr
a0

Zr
a0

a0

4 0 2
me e 2

0.5 A

)e Zr / 2 a0

e Zr / 2 a0

P460 - 3D S.E.

21

H Atom Wave Functions

P460 - 3D S.E.

22

H Atom Degeneracy
As energy only depends on n, more than one state with same energy for n>1 (only first
order)
ignore spin for now
Energy
n
l
m
D

-13.6 eV

0(S)

-3.4 eV

1(P)

-1,0,1

1 Ground State
4 First excited states
9 second excited states

-1.5 eV

3
1

D n2

2(D)

P460 - 3D S.E.

3
1

-1,0,1

-2,-1,0,1,2

23

Probability Density
| |2 probabilit y
2
|

|
dVolume 1 normalization

or
0

2
2
|

|
r
sin d d dr

| |

r 2 d d cos dr

P ( r ) r 2 | Rnl |2
P is radial probability density
small r naturally suppressed by phase space (no volume)
can get average, most probable radius, and width (in r) from P(r). (Supplement 8-A)

most probable

dP
dr

average r r
width r

P460 - 3D S.E.

r2 r 2

24

Most probable radius

For 1S state

P ( r ) Ar 2 | R |2 Ar 2 e 2 r / a0
dP
dr

0 2 re 2 r / a0
r a0

2r2
a0

e 2 r / a0

(" peak " )

rP ( r )dr

3
2

a0

n a0
l ( l 1)
1
Bohr radius (scaled
for different
levels)
is a good
approximation
of the
average
most probable value---depends
on n
(
[1
)]
in orgeneral
)
Z
2 (1
n2
and L
2 r / a0
2
r 2 spread
out
r 2with
Awidth
r 2e
but electron probability
about the samedr
size 3a0

3a02

9
4

a02 0.87 a0

P460 - 3D S.E.

25

Radial Probability Density

P460 - 3D S.E.

26

Radial Probability Density

note #
nodes

P460 - 3D S.E.

27

Angular Probabilities
P ( , ) | ( ) |2 | ( ) |2 sin( )
m e im | |2 1

no phi dependence. If (arbitrarily) have phi be angle around z-axis, this

means no x,y dependence to wave function. Well see in angular
momentum quantization
00 "1"

S states

10 A cos

11

A
2

sin

P states

2
2
10
12, 1 11
"1"

L=0 states are spherically symmetric. For L>0, individual states are
squished but in arbitrary direction (unless broken by an external field)
Add up probabilities for all m subshells for a given L get a spherically
symmetric probability distribution

P460 - 3D S.E.

28

Orthogonality
nlm nl m

0 0

nn ' ll ' mm '

*
2

r
sin dr d d
nlm
n
'
l
'
m
'

with Rn lm m

each individual eigenfunction is also orthogonal.

Many relationships between spherical harmonics. Important in, e.g.,
matrix element calculations. Or use raising and lowering operators
example

E cons tan t in z
V | E | r cos
note
cos is Legendre polynomial 10
nlm | r cos | n' l ' m'
mm ' l ( l ' 1) f ( r ) 0
m m'

P460 - 3D S.E.

l l '1

29

Wave functions
build up wavefunctions from eigenfunctions.
example
1
( r, , , t )

( 100e iE1t / 2 211e iE2t / 211e iE2t / )

what are the expectation values for the energy and the total and zcomponents of the angular momentum?
E

H |

*
H dvol

*
i

dvol
t

have wavefunction in eigenfunction components

E
L2

Lz

1
1
5
9
( E1 4 E2 E2 )
( E1
E1 )
E1
6
6
4
24
1

( l0 ( l0 1) 4 l1 ( l1 1) l1 ( l1 1))
6
1
10

( 0( 0 1) 4 1(1 1) 1(1 1))

6
6
1
1
3

( Lz 0 4 Lz1 Lz 1 )
( 0 4 1)
6
6
6

P460 - 3D S.E.

30