Lecture 10: Particles in 3D

Potentials and the Hydrogen

Atom
1  r / ao
 ( x , y , z )   ( x ) ( y )  ( z ) (r ) 3
e
a o
z 11 1
r = a0

L P(r)
g( x) 0.5
L
x

00 0
L 0 0 r2 4a0 4
0 x 4

 
2
h 2 2 2  13.6 eV
Enx n y nz   n x  n y  n z En 
8mL2 n2
 Content
 3-Dimensional Potential Well
 Product Wavefunctions
 Concept of degeneracy
 Early Models of the Hydrogen Atom
 Planetary Model
 Quantum Modifications
 Schrödinger’s Equation for the Hydrogen Atom
 Ground state solution
 Spherically-symmetric excited states (“s-states”)
 Quantum Particles in 3D Potentials
 So far, we have considered quantum particles A real (3D)
“quantum dot”
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/)

 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.

 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)
 The extension of the Schrödinger Equation (SEQ) to 3D
is straightforward in cartesian (x,y,z) coordinates:
 2  d 2  d 2  d 2  


 2  2  U ( x , y , z )  E where    ( x , y , z )
2 m  dx 2
dy dz 

like
1 2
2m

p x  p 2y  p z2  Kinetic energy term in the
Schrödinger Equation

 Let’s solve this SEQ for the particle in a 3D box:

z  outside box, x or y or z < 0
U(x,y,z) = 0 inside box
 outside box, x or y or z > L
L
L This simple U(x,y,z) can be “separated”
x
y U(x,y,z) = U(x) + U(y) + U(z)
L
 Particle in a 3D Box (2)
 So the Schrödinger Equation becomes:

 2  d 2  d 2  d 2  
  2  2  U ( x )  U ( y )  U ( z )  E

2 m  dx 2
dy dz 

and the wavefunction    ( x , y , z ) can be “separated”

into the product of three functions:
 ( x , y , z )   ( x ) ( y ) ( z )
 So, the whole problem simplifies into three one-dimensional
equations that we’ve already solved in Lecture 7.
2
 2 d 2  ( x) n   h 2  nx 
  U ( x ) ( x )  E x ( x )  n ( x )  N sin  x x  E nx   
2 m dx 2
 L  2m  2 L 
2
 2 d 2  ( y)  n y  h2  ny 
  U ( y ) ( y )  E y ( y )  n ( y )  N sin  y  E ny   
2 m dy 2
 L  2m  2 L 

..Likewise for (z).. graphic

 Particle in a 3D Box (3)
 So, finally, the eigenstates and associated
energies for a particle in a 3D box are: z
n    n y   n z 
  N sin  x x  sin  y  sin  z L
 L   L   L 
x
Enx n y nz 
h2
8mL 2
 
n x
2
 n y
2
 n z 
2
L
y
where nx,ny, and nz can each have values 1,2,3,…. L

 This problem illustrates 2 important new points.

(1) Three ‘quantum numbers’ (nx,ny,nz) 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
 exercise 1
Consider a particle in a two-dimensional (infinite) well, with Lx = Ly.
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., Lx < Ly) 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)
 exercise
Consider a particle in a two-dimensional (infinite) well, with Lx = Ly.
1. Compare the energies of the (2,2), (1,3), and (3,1) states?
a. E(2,2) > E(1,3) = E(3,1)
E(1,3) = E(1,3) = E0 (12 + 32) = 10 E0
b. E(2,2) = E(1,3) = E(3,1)
E(2,2) = E0 (22 + 22) = 8 E0
c. E(1,3) = E(3,1) > E(2,2)

2. If we squeeze the box in the x-direction (i.e., Lx < Ly) compare

E(1,3) with E(3,1): The tighter confinement along x will increase
the contribution to E. The effect will be
a. E(1,3) < E(3,1) greatest on states with greatest nx:
b. E(1,3) = E(3,1)
h 2  nx 2 n y 
2

c. E(1,3) > E(3,1) E nx n y   2  2 

Example: Lx = Ly/2
8m  Lx L y 

h2
E( nx n y ) 
8 mL y 2
  4 n x
2
 n y
2
  E (1,3)  4  9; E (3,1)  36  1
 Energy levels
 Now back to a 3D cubic box: z

Show energies and label (nx,ny,nz) for the first L

11 states of the particle in the 3D box, and
write the degeneracy D for each allowed energy. x
Use Eo= h2/8mL2. L
y
L
E
 Energy levels
 Now back to a 3D cubic box: z

Show energies and label (nx,ny,nz) for the first L

11 states of the particle in the 3D box, and
write the degeneracy D for each allowed energy. x
Use Eo= h2/8mL2. L
y
L
E (nx,ny,nz)
E nx n y nz 
h2
8 mL2
n 
x
2
 n y
2
 n z
2

nx,ny,nz = 1,2,3,...

6Eo (2,1,1) (1,2,1) (1,1,2) D=3

3Eo (1,1,1) D=1

 Another 3D System: The Atom
-electrons confined in Coulomb field of a nucleus
Early hints of the quantum nature of atoms:
 Discrete Emission and Absorption spectra Atomic hydrogen
 When excited in an electrical discharge, atoms
emitted radiation only at discrete wavelengths
 Different emission spectra for different atoms 
 (nm)

 Geiger-Marsden (Rutherford) Experiment (1911):

Au
 Measured angular dependence of  particles (He ions) scattered from
gold foil.  
 Mostly scattering at small angles  supported the “plumvpudding”
model. But…
 Occasional scatterings at large angles Something massive in there!
 Conclusion: Most of atomic mass is concentrated in a small region
of the atom
a nucleus!
 Atoms: Classical Planetary Model
(An early model of the atom)

 Classical picture: negatively charged objects -e

(electrons) orbit positively charged nucleus due to F
Coulomb force.
 There is a BIG PROBLEM with this:
+Ze
 As the electron moves in its circular orbit, it is
ACCELERATING.
 Accelerating charges radiate electromagnetic
energy.
 Consequently, an electron would continuously lose
energy and spiral into the nucleus in about 10-9 sec.

The planetary model doesn’t lead to stable atoms.

 Can the wave nature of the electron
eliminate the radiation problem?
What if the electron assumed a ‘stationary quantum state’ (like the
particle states in our hypothetical boxes)? Since the probability density
is static for a stationary state, there would be no radiation of energy.
The stability problem would be solved!
Is it possible to find a stationary state for the coulomb potential?
Before Schrödinger (but after DeBroglie), you might have tried the
following “semi-classical” approach (just as Neils Bohr did, and for
which he got the Nobel prize in 1922):
p
-e
-e 
Instead r Imagine
of this: this: +Ze
+Ze

For a ‘standing wave’, the number of

wavelengths equals the circumference:
n= 2r A proper description requires
This is valid only for large n the Schrödinger Equation…
(Correspondence Principle); see Appendix
http://www.colorado.edu/physics/2000/quantumzone/debroglie.html
 Potential Energy for the Hydrogen Atom (1)
 How do we describe the hydrogen atom quantum
mechanically?
 We need to specify U, the potential energy of the electron: U(r)
We assume that the Coulomb force between the electron and the
nucleus is the force responsible for binding the electron in the atom
0 r

e 2
U( r )   1
r   9  10 9 Nm 2 / C 2
4  0

 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

This spherically symmetric problem must be solved in

spherical coordinates.
 Product Wavefunction in Spherical Coordinates
 The solution to the SEQ in spherical coordinates
is a product wave function of the form:

 n lm ( r ,  ,  )  R n l ( r )Y lm ( ,  ) r z
y
with quantum numbers: n l and m
x 
principal orbital magnetic
(angular
momentum)
Rnl is the ‘radial part’, and Ylm are “spherical harmonics.” The
Schrödinger 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:
  2 1 2 s-state
e 2 
 r  Rn 0 ( r )  E n Rn 0 ( r ) Wavefunction:
 2 m r r 2 r 
  ( r , , )  R n 0 ( r )
KE term PE term
 Radial Eigenstates of H

The radial eigenstates, Rno(r) , for the electron in the
Coulomb potential of the proton are plotted below:
“s-state” wavefunctions
The zeros in the subscripts below are a reminder that these are states with zero angular momentum.

1 1 1 1 3

2
R10 R20
f( x) 0.5 h( x)
0.5
d4( x) R30

0 0
0 00 .2 .50
0 15a
00 2 4
4a0 00 5 10a
10 00 5
r 10 15 0
0 rx 4 0 rx 10
0
0 x 15
2
  2 r  r  
r   r / 2 a0    e  r / 3 a0
R1,0 ( r )  e  r / a0 R2,0 ( r )   1   e R3, 0 ( r )  3   2

 2 a0  
a0  3a 0  

2
a0  = “Bohr radius” = 0.053 nm
me 2  e 2 1  13 .6 eV
En  
Plug these into radial SEQ (Appendix)  2 ao n 2 n2
 Probability Density of Electrons
Probability density = Probability per unit volume = 2  Rn02 for s-states
The density of dots plotted below is proportional to Rn02.
“1s state” “2s state”

1 1 1 1

R10 0.5 R20

f( x) 0.5 h( x)

0
.2
0 00 0
00 00 5 10a
10
2
rx
4
4a0 0 rx 10
0
0 4
 Radial Probability Densities for s-states
 Summary of wave functions and radial probability densities
for some s-states:

1 1 1 1
P10
R10
f( x) 0.5 g( x) 0.5
Question: If the
classical planetary
0 0 0
model were
00 0 00
00 2
r
x
4a
4 0
4
00
2
r
x 4a
4 0
4
correct, then
1 1
.5
what would you
R20 0.4 P20 expect for P(r)?
0.5
h( x)
h2( x)
0.2

00
.2

000 5
10a
10
0
00 0 10a
r x 10 0
0
0 rx5 10
10 0
3

P30
2
R30
d4( x)

0
.5
0
0 00 5
rx
10
15a
15
15 0 0 r 20a0

radial wave functions radial probability densities, P(r)

 Optical Transitions in H -- Example
 An electron, initially excited to the n = 3 r/a0
energy level of the hydrogen atom, falls 00 5 10 15
20
20

to the n = 2 level, emitting a photon in 00

the process. What are the energy and E3
wavelength of the photon emitted?
-5 E2
E (eV)
U(r)
-10

-15-15 E1

Atomic hydrogen


 (nm)

Answer: 656 nm
Discharge tubes
 Optical Transitions in H --Example
 An electron, initially excited to the n = 3 r/a0
energy level of the hydrogen atom, falls 00 5 10 15
20
20

to the n = 2 level, emitting a photon in 00

the process. What are the energy and E3
wavelength of the photon emitted?
-5 E2
 13.6 eV E (eV)
En 
n2 -10
U(r)
Therefore:
 1 1 
 E ni  n f   13.6  2  2  eV -15-15 E1
n
 i nf 
1 1 Atomic hydrogen
E photon   E 3 2   13.6    eV  1.9eV
9 4
hc 1240eV  nm
   656nm 
 (nm)
E photon 1.9eV

You will experimentally measure several transitions in Lab.

 Ground-state wavefunction for
H
1) What is the— three standard
normalization problems
constant N?
 ( r )  N e  r / ao
Standard procedure:
1 1

a) The probability density is  2 = N2 exp(-2r/ao). rR10 (r)

This is the “probability per unit volume”. f( x) 0.5

b) Integrate over volume:Probability =   2 dV = 1

0 00

c) For spherical symmetry, dV = 4r2 dr 00 2 4a

4
0
0 x 4

2 2  2 r / ao 2 1
4N r e dr  1 yields N  3
a o
(integral table)
0

1  r / ao Ground-state wavefunction
(r ) 3
e
a o for hydrogen
 Ground-state wavefunction for
H
—three standard problems
1 1
2) Estimate the probability of finding
the electron within a small sphere of rR10 (r)
radius rs = 0.2 ao at the origin. f( x) 0.5
rs
a) If it says “estimate”, don’t “integrate”. 0 00
00 2 4a
4
0
b) The wavefunction is nearly constant near r = 0: 0 x 4

 ( r )  N e  r / ao
1 0 / ao 1
 (0 )  3
e 
a o a o3
c) Simply multiply  2 by the volume V = (4/3) rs3.

2
Probabilit y   ( 0 )  V 

Answer: 1.07 %
 Ground-state wavefunction for
H
—three standard problems
1 1
2) Estimate the probability of finding
the electron within a small sphere of rR10 (r)
radius rs = 0.2 ao at the origin ? f( x) 0.5

rs
a) If it says “estimate”, don’t “integrate”. 0 00
00 2 4a
4
0
0 x 4
b) The wavefunction is nearly constant near r = 0:
 ( r )  N e  r / ao
1 0 / ao 1
 (0 )  3
e 
a o a o3

c) Simply multiply  2 by the volume V = (4/3) rs3 .

3
2 4  rs 
Probabilit y   ( 0 )  V    = 0.0107
3  ao 
 Ground-statewavefunction
Ground-state wavefunctionfor
forH
H
—three standard problems
3) At what radius are you most likely 1 1

to find the electron?  ( r )  N e  r / ao

Looks like a no-brainer. r = 0, of course! f( x) 0.5

Well, that’s not the answer. You must find the r

probability P(r)r that the electron is in a shell 0 00
rmax
00 2 4a
4
of thickness r at radius r. The volume of the 0 x
0
4

shell V increases with radius: rmax = ?

2
Probability  P(r) r   ( r ) V 1 1
1
P(r)r
2 - 2r/ao
 Cr e r  4r22
P(r)
g( x) 0.5
r Set dP/dr = 0 to find rmax

r 0 0
0
00 r2 4a
4
0
0 x 4

V = 4r2 r rmax = Answer: ao

 Example Problems (1)
a) What is the energy of the second excited state of a 3-D
cubic well?
b) How many states have this energy?

Answer: 9 Eo, 3
 Example Problems (1)
a) What is the energy of the second excited state of a 3-D
cubic well?
b) How many states have this energy?

Solution: Starting with E211 (the first

a) E311 = (32+12+12) Eo = 11 Eo
E221 = (22+22+12) Eo = 9 Eo
with Eo= h2/8mL2
b) 
excited state), we must
increase one of the quantum
numbers. Which choice adds
the least energy? E221 or E311?
There are three distinct ways
to arrange the three numbers,
2, 2, and 1.
The different arrangements
correspond to different x, y,
and z components of the
momentum.
 Example Problems (2)
Consider the three lowest energy states of the hydrogen
atom. What wavelengths of light will be emitted when
the electron jumps from one state to another?

Answer: 122 nm, 102 nm, 653 nm

 Example Problems (2)
Consider the three lowest energy states of the hydrogen
atom. What wavelengths of light will be emitted when
the electron jumps from one state to another?

Solution:
E21 = 10.2 eV E = -13.6 eV/n2, so E1 = -13.6 eV, E2 = -3.4 eV,
and E3 = -1.5 eV. There are three jumps to
E31 = 12.1 eV
consider, 2-to-1, 3-to-1, and 3-to-2. The
E32 = 1.9 eV photon carries away the energy that the
electron loses.
 = h/p = hc/E
hc = 1240 eV·nm
21 = 122 nm
Two wavelengths are all in the ultraviolet.
31 = 102 nm Note that the 3-to-2 transition gives a
32 = 653 nm visible (red) photon, 32 = 653 nm.