Born’s interpretation of the

wave function
It is not possible to measure all properties of
Physical Chemistry a quantum system precisely
Max Born suggested that the wave function
was related to the probability that an
Lecture 13 observable has a specific value.
The Meaning of Wave Functions; Often called the Copenhagen interpretation
Solving Complex Problems A parameter of interest is position (x,y,z)

 * ( x , y , z )  ( x , y , z ) d 3r  P ( x , y , z ) d 3r

Requirements on a wave
function Example: particle in a 1-D box
To be consistent with the Born
interpretation, a wave function has to Wave functions
have certain characteristics.
 Square integrable over all space. (In this way it
can be normalized and represent probability.)
 Single-valued (so that the probability at any point
is unique)
 Continuous at all points in space. Square of wave
 First derivative must be continuous at all points functions
where the potential is continuous.

Expectation values for a Expectation values for a

particle in a 1-D box particle in a 1-D box
nx nx Expectation value of
a
Expectation value of 2 nx d nx
a
2i
a 0
x 
a 0
sin( ) x sin( )dx  px    sin( ) sin( )dx
the position a a the momentum a dx a
n
2in nx nx
a
2a
 y sin a 2 0
 2
ydy   sin( ) cos( )dx
n 2 2 0
a a

a  0

2
nx 2 nx
a
2
Expectation value of nx d 2 nx
a 0
a
 x2   2 2
Expectation value of sin(
a
) x sin(
a
)dx  px2   
a 0
sin( )
a dx 2
sin( ) dx
the square of the
a
the square of the n 2 2 n
n
2a 2 momentum   sin
y
2
position  2
sin 2 ydy a2
ydy
n 3 3 0
0
 An eigenvalue (!!!) n 
2 2 2

1 1  Must be an eigenstate a2
 a2   
3 2n 2 2  of px2

1
Copenhagen interpretation for an
arbitrary (mixed) state Particle in a 3-D box
Particle in a 1D box in
an arbitrary state 2  nx  The actual space in which we live is
 written as a sum of the
 ( x)  c n sin  

energy eigenstates
n a  a  three-dimensional.
The expectation value General problem of a particle in a 3-D
of the energy of the
a
E   ( x) H ( x)dx
box is appropriate to gas molecules
*

particle in this state is a 0

sum of contributions  j x   kx 

Example of a complex problem
a
2
 Importantly, if one
  c*j ck  sin a  H sin a dx
a j ,k
decomposed into a simpler problem
0
determines the 2  jx   kx 
a

expectation value by   c*j ck Ek  sin a  sin a dx

Hamiltonian
a j ,k
repeated measurements, 0

one ONLY finds among  c c E  *

2  2 2 2 
j k k jk
H      
the measurements
2m  x 2 y 2 z 2 
j ,k

elements of {Ek}  c c E
k
*
k k k  p E
k
k k

Application to the particle in a

Separation of variables 3-D box
There is only one way for the following kind Overall problem may be
of equation to be generally satisfied separated into three 1- H ( x, y, z ) ( x, y, z )  E ( x, y, z )
D problems
Hamiltonian must be a H x ( x)x ( x)  E x x ( x)
f ( x)  g ( y ) sum of Hamiltonians H y ( y )y ( y )  E y y ( y )
H z ( z )z ( z )  E z z ( z )
Each depends on a single
f ( x)  C

independent variable
H ( x, y , z )  H x ( x)  H y ( y)  H z ( z )
The wave function is a
g ( y)  C product of wave E  Ex  Ey  Ez
functions for each mode
Each function must be equal to a constant, The energy is a sum of  ( x, y, z )  x ( x)y ( y )z ( z )

independent of either x or y the energies of the

modes

Solutions to the particle in a Probability plots for a particle

3-D box in a 2-D box
Each mode is exactly like the particle in Upper graph
a 1-D box  nx = 1
Solutions and energies of these modes  ny = 1
Lower graph
are known  nx = 1
Overall solution  ny = 2 f

Note the symmetry of the

 n x   n yy   nzz 
3
2 graphs and how it changes
nx n y nz ( x, y, z )  sin  x  sin   sin  
abc  a   b   c  depending on the
relationship of the
h 2  nx2 n y nz2 
2

En x n y n z   2 2 eigenvalues
8m  a 2
b c 
g

2
Symmetry and degeneracy Quantum model problems
For the particle in a 3-D box, the energies System Model
Potential Differential
Solutions
depend on the size of the box in each
Energy Equation

direction
Bounded
Particle in a
Gas molecule Either 0 or  wave Sines and cosines
Box
equations

When a = b  c, the states (1,2,nz) and Bond vibration

Harmonic
(k/2)(r-req)2
Hermite’s
Hermite polynomials
(2,1,nz) necessarily have the same energy oscillator equation

Spherical
Symmetry increases the number of states at Molecular rotation Rigid rotor
Either 0 or  harmonic
(angular
Spherical harmonic
functions

a particular energy momentum)

Legendre
 Degeneracy increases because of symmetry Central-force
Legendre’s
and
polynomials,
Laguerre
Hydrogen atom -Ze2/r
Very important relation used to determine
problem Laguerre’s polynomials,
 equations spherical harmonic

symmetry properties of systems

functions

Multi-mode Complicated Complex products of

Complex systems Complex
systems equations functions

Summary
A system’s wave function provides all possible information
on it
The wave function provides probabilities for values of
properties
 Born (Copenhagen) interpretation
 When a system is in an eigenstate, the value is exact
 Repeated measurements give the same result for the property’s
value
 Example: particle in a 1-D box
 Probability of position found from the square of the normalized
wave function for that position
 States are not eigenfunctions of position
 Expectation value for the position by averaging over probability
 Energy eigenstate is also an eigenstate of px2
Particle in a 3-D box
 Example of decomposition of a complex problem into simpler
problems
 Symmetry and degeneracy of energy levels