QM Reminder

C Nave @ gsu.edu

http://hyperphysics.phy-astr.gsu.edu/hbase/quacon.html#quacon
 Outline
• Postulates of QM
• Picking Information Out of Wavefunctions
– Expectation Values
– Eigenfunctions & Eigenvalues
• Where do we get wavefunctions from?
– Non-Relativistic
– Relativistic
• What good-looking s look like
• Techniques for solving the Schro Eqn
– Analytically
– Numerically
– Creation-Annihilation Ops
 Postulates of Quantum Mechanics
• The state of a physical system is completely described by a
wavefunction .
• All information is contained in the wavefunction 

• Probabilities are determined by the overlap of

wavefunctions
2
 a | b 
 Postulates of QM

• Every measurable physical quantity has a corresponding operator.

• The results of any individ measurement yields one of the

eigenvalues n of the corresponding operator.

• Given a Hermetian Op with eigenvalues n and eigenvectors n ,

the probability of measuring the eigenvalue n is

2 2

*
n  d r
3
or n 
 Postulates of QM
• If measurement of an observable gives a result n , then
immediately afterward the system is in state n .

• The time evolution of a system is given by

d
• . i   H 
dt

corresponds to
classical Hamiltonian
Picking Information out of
Wavefunctions

Expectation Values
Eigenvalue Problems
 Common Operators
• Position
r = ( x, y, z ) - Cartesian repn

• Momentum
p   i    i  (  x ,  y ,  z )

• Total Energy
Etot  i  t
op

• Angular Momentum
L=rxp - work it out
 Using Operators: A
• Usual situation: Expectation Values
A  
all space
 * A  d 3r

• Special situations: Eigenvalue Problems

A   
the original wavefn
a constant
(as far as A is concerned)
 Expectation Values
• Probability Density at r

  (r )  (r )

• Prob of finding the system in a region d3r about r

  d 3r
• Prob of finding the system anywhere

 
all space
 d 3r  1
• Average value of position r



 r  d 3r
all space

• Average value of momentum p




 p  d 3r
all space

• Expectation value of total energy


all space
 H  d 3r
 Eigenvalue Problems

Sometimes a function fn has a special property

 some const 
Op fn    fn
 wrt the Op 

eigenvalue eigenfn

Since this is simpler than doing integrals, we usually label QM systems

by their list of eigenvalues (aka quantum numbers).
 Eigenfns: 1-D Plane Wave moving in +x direction

x,t = A sin(kx-t) or A cos(kx-t) or A ei(kx-t)

•  is an eigenfunction of Px
Px    i x ei ( kx t )  k e i ( kx  t )  k 

•  is an eigenfunction of Tot E
Tot E   i t ei ( kx t )   ei ( kx t )   

•  is not an eigenfunction of position X

X  x ei ( kx t )  x
 Eigenfns: Hydrogenic atom nlm(r)
•  is an eigenfunction of Tot E
 P2 
Tot E nlm (r )  H nlm (r )     V  nlm (r )
 2m 
mZ 2 e 4 1 Z2
  nlm (r )   2 13.6 nlm (r )
(4 o ) 2 n
2 2 2
n
•  is an eigenfunction of L2 and Lz
units eV

L2 nlm (r )  (  1) 2 nlm (r )

• L z ofnlmparity
 is an eigenfunction (r )  m 2 nlm (r )

Parity nlm (r )  () nlm (r )

 Eigenfns: Hydrogenic atom nlm(r)

•  is not an eigenfn of position X, Y, Z

•  is not an eigenfn of the momentum vector Px , Py , Pz

•  is not an eigenfn of Lx and Ly

Where Wavefunctions come
from
Where do we get the wavefunctions from?

• Physics tools
– Newton’s equation of motion
– Conservation of Energy
– Cons of Momentum & Ang Momentum

The most powerful and easy to use technique is Cons NRG.

 Schrödinger Wave Equation
Use non-relativistic formula for Total Energy Ops

p2
H  KE  V   V and
op
Etot  i  t
2m

H   r, t   i  t   r, t 

 p2 
  V    r, t   i  t   r, t 
 2m 

 2 2 
   V    r, t   i  t   r, t 
 2m 
http://www-groups.dcs.st-and.ac.uk/~history/Mathematicians
 Klein-Gordon Wave Equation
Start with the relativistic constraint for free particle:
Etot2 – p2c2 = m2c4 .

p2 = px2 + py2 + pz2

[ Etot2 – p2c2 ] (r,t) = m2c4 (r,t).

  i  
t
2
   i   c 2
2
  r, t   m 2c 4  r, t 

 a Monster to solve
 Dirac Wave Equation
Wanted a linear relativistic equation
Etot2 – p2c2 = m2c4
p = ( px , py , pz )
[ Etot2 – p2c2  m2c4 ] (r,t) = 0

Change notation slightly


p0  Etot
op
/ c  i t
c
P4 = ( po , ipx , ipy , ipz )
~ [P42c2  m2c4 ] (r,t) = 0
difference of squares can be factored ~ ( P4c + mc2) (P4c-mc2)
and there are two options for how to do overall +/- signs
 4 coupled equations to solve.
Time Dependent Schro Eqn

d
i   H 
dt
Where H = KE + Potl E

  x, t 
 ER 5-5

Time Dependent Schro Eqn

d
i   H 
dt Where H = KE + Potl E
 p2 
  V    r, t   i  t   r, t 
 2m 
 2 2 
   V    r, t   i  t   r, t 
 2m 

  x, t 
 Time Independent Schro Eqn

KE involves spatial derivatives only

If Pot’l E not time dependent, then Schro Eqn separable

  x, t     x f t
ref: Griffiths 2.1

  x, t     x e  iEt / 
  2 2 
   V    r, t   i  t   r, t 
 2m 

 2 2 
   V    r   Etot  r 
 2m 

Drop to 1-D for ease

 2 2 
  x  V  x   x  Etot  x 
 2m 
 ER 5-6

What Good Wavefunctions Look

Like
 Sketching Pictures of Wavefunctions

Prob ~  KE + V = Etot

 KE  V  x    x   Etot  x

 p2 
  V  x     x   Etot  x
 2m 

 2 2 
  x  V  x   x   Etot  x
 2m 
Bad Wavefunctions
 Sketching Pictures of Wavefunctions
 2 2 
  x  V  x   x  Etot  x
 2m 
To examine general behavior of wave fns, look for soln of the form

  Ae ik x

where k is not necessarily a constant

(but let’s pretend it is for a sec)

 2k 2
 V  Etot
2m KE

2m
k  2
 Etot  V 

   Ae ik x

2m
k  2
 Etot  V 

KE + KE 
If Etot > V, then k Re If Etot < V, then k Im

 ~ kinda free particle  ~ decaying exponential

2/k ~  ~ wavelength /k ~ 1/e distance

 Sample (x) Sketches

• Free Particles
• Step Potentials
• Barriers
• Wells
Free Particle
Energy axis

V(x)=0 everywhere
1-D Step Potential
1-D Finite Square Well
1-D Harmonic Oscillator
1-D Infinite Square Well
1-D Barrier
NH3 Molecule
 E&R Ch 5 Prob 23

Discrete or Continuous Excitation Spectrum ?

 E&R Ch 5,
Prob 30

Which well goes with wfn ?

Techniques for solving the Schro Eqn.

• Analytically
– Solve the DiffyQ to obtain solns

• Numerically
– Do the DiffyQ integrations with code

• Creation-Annihilation Operators
– Pattern matching techniques derived from 1D SHO.
 Analytic Techniques

• Simple Cases
– Free particle (ER 6.2)
– Infinite square well (ER 6.8)
• Continuous Potentials
– 1-D Simple Harmonic Oscillator (ER 6.9, Table 6.1, and App I)
– 3-D Attractive Coulomb (ER 7.2-6, Table 7.2)
– 3-D Simple Harmonic Oscillator
• Discontinuous Potentials
– Step Functions (ER 6.3-7)
– Barriers (ER6.3-7)
– Finite Square Well (ER App H)
 Eigenfns: Bare Coulomb - stationary states
nlm(r) or Rnl(r) Ylm()

Simple/Bare
Coulomb
 Numerical Techniques
ER 5.7, App G

• Using expectations of what the wavefn should look like…

– Numerical integration of 2nd order DiffyQ
– Relaxation methods
– ..
– ..
– Joe Blow’s idea
– Willy Don’s idea
– Cletus’ lame idea
– ..
– ..
 SHO Creation-Annihilation Op
Techniques
Define: 1
aˆ 
1
 ipˆ  m xˆ  aˆ     ipˆ  m xˆ 
2m 2m

 x, pˆ   i  aˆ, aˆ   1


pˆ 2 1 2
H   ( a  a  12 )   kx
2m 2

If you know the gnd state wavefn o, then the nth excited state is:

  ˆa  n
o
 Inadequacy of Techniques
• Modern measurements require greater accuracy in
model predictions.
– Analytic
– Numerical
– Creation-Annihilation (SHO, Coul)
• More Refined Potential Energy Fn: V()
– Time-Independent Perturbation Theory
• Changes in the System with Time
– Time-Dependent Perturbation Theory