Topic 5: Schrödinger Equation

• Wave equation for Photon vs. Schrödinger equation for Electron+

• Solution to Schrödinger Equation gives wave function 
– 2 gives probability of finding particle in a certain region
• Square Well Potentials: Infinite and Finite walls
–  oscillates inside well and is zero or decaying outside well, E  n2
• Simple Harmonic Oscillator Potential (or parabolic)
–  is more complex, E  n

Example Infinite Well Solution

Page 1
 Schrödinger Equation
• Step Potential of Height V0
–  is always affected by a step, even if E > V0
– For E > V0,  oscillates with different k values outside/inside step.
– For E < V0,  oscillates outside step and decays inside step.

• Barrier Potential of Height V0

–  oscillates outside and decays inside barrier.

• Expectation Values and Operators

• Appendix: Complex Number Tutorial

Page 2
 Wave Equation for Photons: Electric Field E
2 E 1 2 E
 2 2
x 2
c t
2nd space derivative 2nd time derivative

Propose Solution: E  x, t   E0 cos  kx  t 

Calculate Derivatives:
2 E 2 E
  2
E cos  kx   t    2
E  x, t    k 2
E  x, t 
t x
2 0 2

After Substitution:
2
k 2  
c2
  kc  E  pc where E   and p  k
Page 3
 Schrödinger Eqn. for Electrons+: Wave Function 
2
 2   x, t    x, t 
  V  x, t    x , t   i
2m x 2
t
2nd space derivative 1st time derivative
Propose Simple Solution for constant V:
  x, t   Ae   A cos  kx   t   i sin  kx   t  
i kx  t 

Calculate Derivatives:
 2 
 i Ae 
i kx  t 
 i    i  kx  t 
  
2 2
ik Ae k
t x 2

After Substitution:
2

2m
    V0   i  i  
 k 2

2
k2  Ek  Vo  ETOT
 V0  
2m where E   and p  k
Page 4
 Schrödinger Equation: Applications
• Now, find the eigenfunctions  and eigenvalues E of the Schrödinger
Equation for a particle interacting with different potential energy
shapes. (assume no time dependence)
2
  ( x)
2
  V ( x) ( x)  E  ( x)
2m x 2
• Possible potential energies V(x) include:
• Infinite and Finite square wells (bound particle).
• Simple Harmonic or parabolic well (bound particle).
• Step edge (free particle).
• Barrier (free particle).

Page 5
 Schrödinger Equation: Definitions

• Wave function  has NO PHYSICAL MEANING!

• BUT, the probability to find a particle in width dx is given by:

 x, t   x, t  dx    x, t 
2
P( x, t )dx   
dx

• Normalization of 
– Probability to find particle in all space must equal 1.
– Solve for  coefficients so that normalization occurs.



  
 x   x dx  1

Page 6
 Infinite Square Well Potential: Visual Solutions

Wave and Probability Solutions Energy Solutions

n(x) n2(x)
n=3

n=2

n=1

 nx 
2
k2   
2 2

 n x  
2 En  n 
2
sin   2 
L  L  2m  2 mL 
Page 7
 Infinite Square Well: Solve general  from S.Eqn.

 2 d 2 x 
Inside Well:  2
 E x 
(V = 0) 2m dx
2
2mE  p 
  x   k   x 
" 2
where k  2  
2

 

Oscillatory  x  A1 sin kx  A2 coskx

Outside Well:  x   0  cannot penetrate barriers!

(V = )

Page 8
 Infinite Square Well: Satisfy B.C. and Normalization
• Satisfy boundary conditions  x  A1 sin kx  A2 coskx
 0  0  L  0
n
A2 cos0  0  A2  0 A1 sin kL  0  kL  n  k n 
L

 2k 2 2   
2 2
En   n  
2  Quantized Energy Solutions
2m  2mL 

 nx 
L

  dx  0 An sin  L dx  1

 2
• Satisfy normalization 2


An 
2  x
 sin md  
2
using identity and
L 0
2 L
 nx 
 n x  
2
sin   Wave Solutions
L  L 
Page 9
 Finite Square Well Potential: Visual Solutions

Wave and Probability Solutions Energy Solutions

“leaks” High energy
E
n=3 n(x) outside barrier n2(x) particles
“escape”
Vo

E3

n=2 E2
E1

n 2 2 2
n=1 En  2
 2
2m  L  
 k2 

Energy vs. width: http://www.kfunigraz.ac.at/imawww/vqm/pages/supplementary/107S_07a.html

Energy vs. height: http://www.kfunigraz.ac.at/imawww/vqm/pages/supplementary/107S_07b.html Page 10
 Finite Square Well: Solve general  from S.Eqn.

 2 d 2 x 
Inside Well:  2
 E x 
(V = 0) 2m dx
2mE
 "
 x   k1   x 
2
where k1 2
2

Oscillatory   x   A1 sin  k1 x   A2 cos  k1 x 

2m
Outside Well: 
"
 x   k2   x 
2
where k2 2
2
Vo  E   0
(V = Vo)
Decaying   x   B1ek2 x  B2 ek2 x  can penetrate barriers!
x  a  x  a 
Page 11
 Finite Square Well: Example Problem

(a) Sketch the wave function (x) for the n = 4 state for the finite square
well potential.
(b) Sketch the probability distribution 2(x).

 (x)
2
(x) n=4 n=4

L/2
L
x
L/2 L x

Page 12
 Finite Square Well: Example Problem
Sketch the wave function (x) corresponding to a particle with energy E in the
potential well shown below. Explain how and why the wavelengths and
amplitudes of (x) are different in regions 1 and 2.
(x) V1
Region 1 Region 2 E
V2

x1 x2

• (x) oscillates inside the potential well because E > V(x), and decays
exponentially outside the well because E < V(x).
• The frequency of (x) is higher in Region 1 vs. Region 2 because the kinetic
energy is higher [Ek = E - V(x)].
• The amplitude of (x) is lower in Region 1 because its higher Ek gives a
higher velocity, and the particle therefore spends less time in that region.
Page 13
 Simple Harmonic Well Potential: Visual Solutions
Wave and Probability Solutions
n(x) n2(x) Energy Solutions
n=2 (different well widths)

n=1

 1
n=0 En   n   
 2

Page 14
 Simple Harmonic Well: Solve  from S.Eqn.
NEW!

Inside Well:  " x   k 2 x  where k 2  2m  E  V  x 

2  
(x) is not a simple trigonometric function.

2m
Outside Well:  "  x    2  x  where  2  [V ( x)  E ]  0
2

(x) is not a simple decaying exponential.

 ( x)  (Hermite Polynomial) (Gaussian Function)

1
  Kx 2   K  2   Kx 2 
 o  Ao exp   ,  1  A1   x exp   , etc.
 2      2  
Page 15
 Step Potential: (x) outside step
2
d 2  x 
S. Eqn:  2
 V ( x)  x   E  x 
2m dx
 2m 
 x   k1  x   2 E
" 2 2
Outside Step: where k1
V(x) = 0  
(x) is oscillatory

Case 1 Case 2

Energy

(x)

Page 16
 Step Potential: (x) inside step
 2m 
Inside Step:  "
 x    k2   x 
2
where k2   2   E  Vo 
2

V(x) = Vo  
(x) is oscillatory for E > Vo
(x) is decaying for E < Vo

Case 1 Case 2

Energy

E > Vo E < Vo

(x)

Scattering at Step Up: http://www.kfunigraz.ac.at/imawww/vqm/pages/samples/107_06b.html

Scattering at Well - wide: http://www.kfunigraz.ac.at/imawww/vqm/pages/supplementary/107S_05d.html
Scattering at Well - various: http://www.kfunigraz.ac.at/imawww/vqm/pages/supplementary/107S_05b.html
Page 17
 Step Potential: Reflection and Transmission

• At a step, a particle wave undergoes reflection and transmission (like

electromagnetic radiation!) with probability rates R and T, respectively.

R(reflection) + T(transmission) = 1
2
 k1  k2  4k1k2
R   T
 k1  k2   k1  k2 
2

• Reflection occurs at a barrier (R  0), regardless if it is step-down

or step-up.
– R depends on the wave vector difference (k1 - k2) (or energy
difference), but not on which is larger.
– Classically, R = 0 for energy E larger than potential barrier (Vo).

Page 18
 Step Potential: Example Problem
A free particle of mass m, wave number k1 , and energy E = 2Vo is traveling
to the right. At x = 0, the potential jumps from zero to –Vo and remains at
this value for positive x. Find the wavenumber k2 in the region x > 0 in
terms of k1 and Vo. In addition, find the reflection and transmission
coefficients R and T.
2mE 2m  2Vo  4mVo
k1    and

2m V  E 2m Vo  2Vo 2m  3Vo  6mVo 3

k2     or k1
2

2
 k1  k2   k1  
2
0.225 
3 2

R   
2 k1
     0.0102 (1% reflected)
 k1  k2   k1  3 
2 k1 
 2.225 

T  1  R  1  0.0102  0.99 (99% transmitted)

Page 19
 Barrier Potential
 2m 
Outside Barrier:   x   k1   x  k1  
" 2 2
2 
where E
 
V(x) = 0 (x) is oscillatory
2m
Inside Barrier:   x   k2   x  where
" 2 k2 
2
2
Vo  E   0
V(x) = Vo (x) is decaying

Energy

Transmission is Non-Zero!

2 k2 a
(x)
Te
http://www.sgi.com/fun/java/john/wave-sim.html
Single Barrier: http://www.kfunigraz.ac.at/imawww/vqm/pages/samples/107_12c.html Page 20
 Barrier Potential: Example Problem
Sketch the wave function (x) corresponding to a particle with energy E in the
potential shown below. Explain how and why the wavelengths and amplitudes of
(x) are different in regions 1 and 3.
 (x) Region 2

Vo

Region 1 Region 3
x
• (x) oscillates in regions 1 and 3 because E > V(x), and decays exponentially in
region 2 because E < V(x).
• Frequency of (x) is higher in Region 1 vs. 3 because kinetic energy is higher there.
• Amplitude of (x) in Regions 1 and 3 depends on the initial location of the wave
packet. If we assume a bound particle in Region 1, then the amplitude is higher there
and decays into Region 3 (case shown above).

Non-resonant Barrier: http://www.kfunigraz.ac.at/imawww/vqm/pages/supplementary/107S_resonance-5.html

Resonant Barrier: http://www.kfunigraz.ac.at/imawww/vqm/pages/supplementary/107S_resonance-6.html
Double Barrier + : http://www.kfunigraz.ac.at/imawww/vqm/pages/supplementary/107S_resonance-0.html Page 21
 Scanning Tunneling Microscopy: Schematic
Tip

Bias voltage VDC

Constant current e- Distance s

contour

Sample
e e
Tunneling current  e -2ks

• STM is based upon quantum mechanical tunneling of electrons across

the vacuum barrier between a conducting tip and sample.
• To form image, tip is raster-scanned across surface and tunneling current
is measured.
Page 22
 STM: Ultra-High Vacuum Instrument
Coarse Motion
Sample

Scanner

Tip

• Well-ordered, clean surfaces for STM studies are prepared in UHV.

• Sample is moved towards tip using coarse mechanism, and the tip is
moved using a 3-axis piezoelectric scanner.
Page 23
 STM: Data of Si(111)7×7 Surface

STM empty

7×7 Unit

18 nm 7 nm
= adatom
• STM topograph shows rearrangement of atoms on a Si(111) surface.
• Adatoms appear as bright “dots” when electrons travel from sample to
tip.
Page 24
 Expectation Values and Operators
• By definition, the “expectation value” of a function is:

 f(x)   x  f x  x dx



• “Operate” on (x) to find expectation value (or average expected
value) of an “observable.”
Observable Symbol Operator
Position x x


 i
Momentum p x
 2 2
Kinetic energy K 2m x 2
 2 2
Hamiltonian H  V  x
2m x 2


Total Energy E i
t Page 25
 Expectation Values: Example Problem
• Find <p>, <p2> for ground state 1(x) of infinite well (n = 1)
0 L

  
L

<p> =   x   i  1  x 


x 
1
0 
-L/2 +L/2
L
 2 x     2 x 
  sin   i   sin  dx
0
L L  x   L L

 x  x  
L
2
   i   sin  cos  dx
L 0
L  L L

<p> = 0 by symmetry (odd function over symmetric limits)

Note: The average momentum goes to zero because the “sum” of positive and
negative momentum values cancel each other out.
Page 26
 Expectation Values: Example Problem, cont.

L
   2 x
 1  x 
 2  1 
 x dx where  1  x  
 2
<p2> = sin
0  x  L L

    
L 2 2

  1  x  1  x    dx where 2 1  x      1  x 

2 

0 L x L

 
2 L

  1  x 1  x dx
 

 L  0
= 1 by normalization

  
2

<p2> =  
 L 

Page 27
 Complex Number Tutorial: Definitions

• Imaginary number i given by: i2 = –1 ( i3 = –i, i4 = 1, i–1 = –i )

• Complex number z is composed of a real and imaginary parts.
2x + iy
Cartesian Form: z = x + iy 5(cos30º + isin30º)
2i
5 ei/6
Polar Form: z = r(cos + i sin
i (2, i)
where r = (x2 + y2)1/2 and tan = y/x
30º or /6
Exponential Form: z = rei 
–1 1 2

–i

Conjugate: z* = x – iy = rcos – i rsin  re– i 

where (z*)(z) = (x – iy)(x + iy) = x2 + y2 (real!)
Page 28
 Complex Number Tutorial: Taylor Series
• Proof of equivalence for polar and exponential forms:

x 2 x3 x 4
exp( x)  1  x     etc.
2! 3! 4!
x2 x4 x3 x5
cos( x)  1    etc. and sin( x)  x    etc.
2! 4! 3! 5!
 x2 x4   x3 x5 
cos x  i sin x  1    etc.   i  x    etc. 
 2! 4!   3! 5! 
x 2 ix3 x 4 ix5
 1  ix      etc.
2! 3! 4! 5!
x 2 ix3 x 4
exp(ix)  1  ix     etc. where i 2  1
2 ! 3! 4!
 exp(ix)  cos x  i sin x

Page 29
Schrödinger Eqn.: Derivation of Space & Time Dependence

2
 2   x, t    x, t  Schrödinger Equation
  V ( x, t )   x, t   i is 2nd Order Partial
2m x 2
t Differential Equation

Assume  is separable
  x, t     x    t 
[i.e. V(x) only]
2
 2  x    t    x    t  Substitution of 
  V ( x)  x    t   i
2m x 2
t

2
d 2  x  d  t 
  t   V ( x)  x    t   i   x  Partial derivatives are
2m dx 2 dt now ordinary derivatives

1 d   x 1 d  t 
2 2

  V ( x)  i Divide by (x)0(t)
2m   x  dx 2
  t  dt
Space dependence ONLY Time dependence ONLY
Page 30
Schrödinger Eqn.: Derivation of Space & Time Dependence

1 d   x 1 d  t 
2 2 Left and right sides have
  V ( x)  i only space (x) and time
2m   x  dx 2
  t  dt (t) dependence now

1 d   x
2 2
Space:   V ( x)  C
2m   x  dx 2
Set each side of equation
1 d  t 
equal to a constant C
Time: i C
  t  dt

d   x
2 2
Space Equation   V ( x)  x   E  x 
 need V(x) to solve! 2m dx 2

Time Solution:  t   e iEt

Check by substitution!

Page 31