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QUANTUM THEORY
OUTLINE
Homework Questions Attached
SECT
TOPIC
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Hermitian Operators
11.
Orthogonality of Wavefunctions
12.
Commutation of Operators
13.
14.
Chapter 2 Homework
1.
Which of the following functions are normalizable over the indicated intervals?
Normalize those functions which can be normalized.
(a) exp(-ax2) (-,); (b) ex (0,); (c) ei (0,2); (d) xe-3x (0,)
2.
3.
4.
True or False
(a) Nondegenerate eigenfunctions of the same operaor are orthogonal.
(b) All Hermitian operators are real.
(c) If two operators commute with a third, they will commute with each other.
(d) d/dx must be continuous as long as the potential, V(x), is finite.
(e) If a wavefunction is simultaneously the eigenfunction of two operators, it will
also be an eigenfuncion of the product of the two operators.
5.
(c) eix
(d) -id/dx
(g) id2/dx2
( x) Ax(a x)
0 xa
Calculate: (a) A; (b) <x >; (c) <p>; (d) <p >
6.
7.
d d
8.
9.
10.
Which of the following functions (defined from - to ) would be acceptable onedimensional wavefunctions for a bound particle.
11.
DATA
h = 6.63x10-34 Js
= h/2 = 1.05x10-34 Js
c = 3.00x108 m/s = 3.00x1010 cm/s
NA = 6.02x1023 mol-1
k = 1.38x10-23 J/K
R = 8.31 J/mol-K
R = 8.31 Pa-m3/mol-K
me = 9.11x10-31 kg (electron mass)
e x dx
1 J = 1 kgm2/s2
1 = 10-10 m
kNA = R
1 amu = 1.66x10-27 kg
1 atm. = 1.013x105 Pa
1 eV = 1.60x10-19 J
1
2
x n e ax dx
n!
a n 1
p 2 (oper ) 2
d2
dx 2
Some Concept Question Topics
Linear operators
Wavefunction orthogonality
Chapter 2
Quantum Theory
Slide 1
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Continued on Second Page
Slide 2
Outline (Contd.)
Orthogonality of Wavefunctions
Commutation of Operators
Differentiability and Completeness of the Wavefunctions
Dirac Bra-Ket Notation
Slide 3
x x+dx
Slide 4
Three Dimensions
Postulate 1: (x,y,z,t) is a solution to the three dimensional Schrdinger
Equation and is a well-behaved, square integrable function.
The quantity, |(x,y,z,t)|2dxdydz = *(x,y,z,t)(x,y,z,t)dxdydz,
represents the probability of finding the particle between
x and x+dx, y and y+dy, z and z+dz.
Shorthand Notation
dz
dx
dy
Two Particles
x
Slide 5
Required Properties of
Finite
Single Valued
(x)
Continuous
(x)
x
Slide 6
Required Properties of
0 as x
y
z
Vanish at endpoints
(or infinity)
Slide 7
No - Multivalued
i.e. x = 1, sin-1(1) = /2, /2 + 2, ...
No - Discontinuous first derivative
at x = 0.
Slide 8
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 9
Operator
Eigenvalue
Eigenfunction
Linear Operators
A quantum mechanical operator must be linear
Operator
Linear ?
x2
Yes
No
log
No
sin
No
Yes
Yes
Slide 11
Operator Multiplication
^
^
First operate with B, and then operate on the result with A.
Note:
Example
Slide 12
Operator Commutation
?
Not necessarily!!
Slide 13
Eigenvalue Equations
Eigenfunction?
Eigenvalue
x2
Yes
sin(x)
No
sin(x)
No
sin(x)
Yes
-2 (All values of
allowed)
Only for
= 1
2 (i.e. 2)
Slide 14
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 15
etc.
Slide 17
Symbol
Operator
Position
Potential Energy
V(x)
V(x)
Momentum
px (or p)
Kinetic Energy
Total Energy
Slide 18
Symbol
Operator
V(x,y,z)
V(x,y,z)
Position
Potential Energy
Momentum
Kinetic Energy
Total Energy
Slide 19
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 20
10
Slide 21
Slide 22
11
On Board
Time Independent
Schrdinger Equation
Slide 23
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 24
12
Continuous Distribution:
P(x)
x x+dx
Slide 25
Positional Averages
Discrete Distribution:
If normalized
If not normalized
If normalized
If not normalized
If normalized
If not normalized
If normalized
If not normalized
Continuous Distribution:
Slide 26
13
Continuous Distribution:
If normalized
Note:
If normalized
<x2> <x>2
Slide 27
Variance
One requires a measure of the spread or breadth of a distribution.
This is the variance, x2, defined by:
Variance
Standard Deviation
Slide 28
14
P(x) = Ax
P(x) = 0
Example
0x10
Calculate: A , <x> , <x2> , x
x<0 , x>10
Note:
Slide 29
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 30
15
Slide 31
The Hamiltonian:
= reduced mass
k = force constant
A Wavefunction:
Slide 32
16
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 33
Integration Limits: -
Slide 34
17
Slide 35
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 36
18
Example
The operator for the total energy of a system is the Hamiltonian.
Show that the HO wavefunction given earlier is an eigenfunction
of the HO Hamiltonian. What is the eigenvalue (i.e. the energy)
Slide 37
Slide 38
19
E = = h
Because the wavefunction is an
eigenfunction of the Hamiltonian,
the total energy of the system
is known exactly.
Slide 40
20
21
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 43
Expectation Values
Postulate 5: The average (or expectation) value of an observable
with the operator is given by
If is normalized
22
Slide 45
<p>
<x2>
<p2>
<KE>
x2
p2
<PE>
Slide 46
23
Slide 47
<x>
<x2>
Also:
Slide 48
24
<p>
Slide 49
<p2>
Also:
Slide 50
25
Uncertainty Principle
Slide 51
<KE>
<PE>
Slide 52
26
<p> = 0
<x2> = 1/(2)
<p2> = 2/2
x2 = 1/(2)
p2 = 2/2
<KE> = = h
<PE> = = h
Slide 53
Outline
Interpretation and Properties of
Operators and Eigenvalue Equations
Operators in Quantum Mechanics
The 1D Schrdinger Equation: Time Depend. and Indep. Forms
Math. Preliminary: Probability, Averages and Variance
Normalization of the Wavefunction
Math. Preliminary: Even and Odd Integrals
Eigenfunctions and Eigenvalues
Expectation Values (Application to HO wavefunction)
Hermitian Operators
Slide 54
27
Hermitian Operators
General
Definition: An operator is Hermitian if it satisfies the relation:
Simplified
Definition (=): An operator is Hermitian if it satisfies the relation:
So what?
Why is it important that a quantum mechanical operator be Hermitian?
It can be proven that if an operator satisfies the simplified definition,
it also satisfies the more general definition.
(Quantum Chemistry, I. N. Levine, 5th. Ed.)
Slide 55
and
a* = a
i.e. a is real
In a similar manner, it can be proven that the expectation values
<a> of an Hermitian operator must be real.
Slide 56
28
Yes.
You are NOT responsible for the proof outlined below, but
only for the result.
Math Preliminary: Integration by Parts
Slide 57
Slide 58
29
or:
Let u = and v = *:
Because and *
vanish at x =
?
Therefore:
Slide 59
The Hamiltonian:
IS Hermitian
Slide 60
30
Outline (Contd.)
Orthogonality of Wavefunctions
Commutation of Operators
Differentiability and Completeness of the Wavefunctions
Dirac Bra-Ket Notation
Slide 61
Orthogonality of Eigenfunctions
Assume that we have two different eigenfunctions of the same
Hamiltonian:
If the two eigenvalues, Ei = Ej, the eigenfunctions (aka wavefunctions)
are degenerate. Otherwise, they are non-degenerate eigenfunctions
We prove below that non-degenerate eigenfunctions are
orthogonal to each other.
Proof:
Slide 62
31
Slide 63
Proof:
If Ej = Ei ,
32
Outline (Contd.)
Orthogonality of Wavefunctions
Commutation of Operators
Differentiability and Completeness of the Wavefunctions
Dirac Bra-Ket Notation
Slide 65
Commutation of Operators
?
Not necessarily!!
If
Slide 66
33
x2
Operators commute
Operators commute
-i
And so??
Why does it matter whether or not two operators commute?
Slide 67
Slide 68
34
Slide 69
Outline (Contd.)
Orthogonality of Wavefunctions
Commutation of Operators
Differentiability and Completeness of the Wavefunctions
Dirac Bra-Ket Notation
Slide 70
35
Slide 72
36
Outline (Contd.)
Orthogonality of Wavefunctions
Commutation of Operators
Differentiability and Completeness of the Wavefunctions
Dirac Bra-Ket Notation
Slide 73
Slide 74
37
Slide 75
38