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Outline of Quantum Chemistry

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You are on page 1of 42

QUANTUM THEORY

OUTLINE

SECT TOPIC

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,)

the indicated interval.

(a) 1/x (0,); (b) (1-x2)-1 (-1,1); (c) e-xcos(x) (0,); (d) tan-1(x) (0,)

(a) i (b) * (take complex conjugate) (c) eix (d) -id/dx

(e) i2d/dx (f) d2dx2 (g) id2/dx2

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.

2 2

Calculate: (a) A; (b) <x >; (c) <p>; (d) <p >

Show that all three functions are orthogonal over the interval [-1,1].

d d

7. Calculate the commutator: , x

dx dx

(a) 3x2d2/dx2; (b) ( )2 (square the function); (c) ( )dx (integrate the function;

(d) exp ( ) (exponentiate the function)

For those that are eigenfunctions, determine the eigenvalues.

(a) e2x; (b) x2; (c) sin(8x); (d) sin(3x) - cos(3x)

11. Which of the following functions (defined from - to ) would be acceptable one-

dimensional wavefunctions for a bound particle.

(a) exp(-ax); (b) xexp(-bx2) ; (c) iexp(-bx2) ; (d) sin(bx)

DATA

h = 6.63x10-34 Js 1 J = 1 kgm2/s2

= h/2 = 1.05x10-34 Js 1 = 10-10 m

c = 3.00x108 m/s = 3.00x1010 cm/s kNA = R

NA = 6.02x1023 mol-1 1 amu = 1.66x10-27 kg

k = 1.38x10-23 J/K 1 atm. = 1.013x105 Pa

R = 8.31 J/mol-K 1 eV = 1.60x10-19 J

R = 8.31 Pa-m3/mol-K

me = 9.11x10-31 kg (electron mass)

2

e x dx

0 2

n!

0

x n e ax dx

a n 1

d2

p 2 (oper ) 2

dx 2

Linear operators

Wavefunction orthogonality

Linear combinations of degenerate wavefunctions

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

1

Outline (Contd.)

Orthogonality of Wavefunctions

Commutation of Operators

Differentiability and Completeness of the Wavefunctions

Dirac Bra-Ket Notation

Slide 3

One Dimension

Equation and is a well-behaved, square integrable function.

the probability of finding the particle between

x and x+dx.

x x+dx

Slide 4

2

Three Dimensions

Equation and is a well-behaved, square integrable function.

represents the probability of finding the particle between

x and x+dx, y and y+dy, z and z+dz.

z Shorthand Notation

dz

dy y

dx

Two Particles

Slide 5

Required Properties of

Finite X

Continuous (x)

be continuous x

Slide 6

3

Required Properties of

Vanish at endpoints 0 as x

(or infinity) y

z

or

Shorthand notation

Slide 7

wavefunctions?

OK

No - Diverges as x -

No - Multivalued

i.e. x = 1, sin-1(1) = /2, /2 + 2, ...

at x = 0.

Slide 8

4

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

One Dimensional Schrdinger Equation

Slide 10

5

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

6

Operator Commutation

?

in opposite orders are the same, the operators

are said to commute with each other.

as shall be discussed later, where we will also give examples.

Slide 13

Eigenvalue Equations

f Eigenfunction? Eigenvalue

3 x2 Yes 3

x sin(x) No

sin(x) No

allowed)

Only for 2 (i.e. 2)

= 1

Slide 14

7

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

Postulate 2: Every observable quantity has a corresponding

linear, Hermitian operator.

is simply multiplication by the position (or function)

^ etc.

obtained by the replacement:

the appropriate context later in the chapter.

Slide 16

8

Derivation of the momentum operator

Wavefunction for a free particle (from Chap. 1)

where

Slide 17

Position x x

Momentum px (or p)

Kinetic Energy

Total Energy

Slide 18

9

Some Important Operators (3 Dim.) in QM

Position

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

The Schrdinger Equation (One Dim.)

Postulate 3: The wavefunction, (x,t), is obtained by solving the

time dependent Schrdinger Equation:

then one can derive a simpler time independent form of the

Schrdinger Equation, as will be shown.

oscillator, atoms, molecules, etc., unless one is considering

spectroscopy (i.e. the application of a time dependent electric

field), the potential energy is, indeed, independent of time.

Slide 21

(One Dimension)

I will show you the derivation FYI. However, you are responsible

only for the result.

On Board

Slide 22

11

= E (the energy, a constant)

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

Math Preliminary: Probability, Averages & Variance

Probability

between x and x+dx

P(x)

x x+dx

Slide 25

Positional Averages

Discrete Distribution:

Continuous Distribution:

Slide 26

13

Continuous Distribution:

If normalized If normalized

Calculate <x> and <x2>

Slide 27

Variance

Below is a formal derivation of the expression for Standard Deviation.

This is FYI only.

This is the variance, x2, defined by:

14

Example

P(x) = Ax 0x10 Calculate: A , <x> , <x2> , x

P(x) = 0 x<0 , x>10

Note:

Slide 29

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

Normalization of the Wavefunction

Slide 31

Lets preview what well learn in Chapter 5 about the

Harmonic Oscillator model to describe molecular vibrations

in diatomic molecules.

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: 0 Integration Limits: -

Slide 34

17

Find the value of A that normalizes the Harmonic Oscillator

oscillator wavefunction:

Slide 35

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

Eigenfunctions and Eigenvalues

Postulate 4: If a is an eigenfunction of the operator with

eigenvalue a, then if we measure the property A for

a system whose wavefunction is a, we always get

a as the result.

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

To end up with a constant times ,

this term must be zero.

Slide 39

E = = h

Because the wavefunction is an

eigenfunction of the Hamiltonian,

the total energy of the system

is known exactly.

Slide 40

20

Is this wavefunction an eigenfunction of the potential energy operator?

be determined exactly.

be determined exactly.

wavefunction is not an eigenfunction of the associated operator.

The method is given by the next postulate.

Slide 41

No. Therefore the momentum of an oscillator

in this eigenstate cannot be measured exactly.

operator?

Yes, with an eigenvalue of h \ , which is just the de Broglie

expression for the momentum.

Thus, the momentum is known exactly. However, the position is

completely unknown, in agreement with Heisenbergs

Uncertainty Principle.

Slide 42

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

with eigenvalue, a, then:

<a> = a

<a2> = a2

a = 0 (i.e. there is no uncertainty in a)

Slide 44

22

Expectation value of the position

average position.

for quantities whose operators involve derivatives, such

as momentum.

Slide 45

earlier examples:

x2 p2 <PE>

Slide 46

23

Preliminary: Wavefunction Derivatives

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

Consider the HO wavefunction we have been using in

earlier examples:

<x> = 0 <p> = 0

x2 = 1/(2) p2 = 2/2

uncertainty principle)

<KE> = = h

<PE> = = h

Slide 53

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 also satisfies the more general definition.

(Quantum Chemistry, I. N. Levine, 5th. Ed.)

Slide 55

Proof: and

a* = a

i.e. a is real

<a> of an Hermitian operator must be real.

Slide 56

28

Is the operator x (multiplication by x) Hermitian? Yes.

the proof

You are NOT responsible for the proof outlined below, but

only for the result.

Math Preliminary: Integration by Parts

Slide 57

?

The question is whether:

?

or:

with: u = and v = *, together with the fact that both and * are

zero at x = . Next Slide

Slide 58

29

?

?

or:

Let u = and v = *:

Because and *

vanish at x =

?

Therefore:

Slide 59

IS Hermitian

parts twice successively)

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

Hamiltonian:

If the two eigenvalues, Ei = Ej, the eigenfunctions (aka wavefunctions)

are degenerate. Otherwise, they are non-degenerate eigenfunctions

orthogonal to each other.

is Hermitian

Slide 62

31

Thus, if Ei Ej (i.e. the eigenfunctions are not degenerate,

then:

they are orthonormal.

Slide 63

Hamiltonian:

combination of i and j is also an eigenfunction of the Hamiltonian

Proof:

If Ej = Ei ,

an eigenfunction of the Hamiltonian.

If we wish, we can use this fact to construct degenerate eigenfunctions

that are orthogonal to each other.

Slide 64

32

Outline (Contd.)

Orthogonality of Wavefunctions

Commutation of Operators

Differentiability and Completeness of the Wavefunctions

Dirac Bra-Ket Notation

Slide 65

Commutation of Operators

?

in opposite orders are the same, the operators

are said to commute with each other.

as shall be discussed below.

Slide 66

33

x x2 0 Operators commute

3 0 Operators commute

And so??

Why does it matter whether or not two operators commute?

Slide 67

^ ^

Lets say that two different operators, A and B, have the

same set of eigenfunctions, n:

operators can be exactly determined simultaneously.

that the two operators commute; i.e.

Conversely, it can be proven that if two operators do not

commute, then the operators cannot have simultaneous

eigenfunctions.

This means that it is not possible to determine both

quantities exactly; i.e. the product of the uncertainties

is greater than zero.

**e.g. Quantum Chemistry (5th. Ed.), by I. N. Levine,

Sect. 5.1

Slide 68

34

We just showed that the momentum and position operators do not

commute:

both be determined exactly; the product of their uncertainties is

greater than 0.

is completely undetermined ( px ), and vice versa.

above for the wavefunction for a Harmonic Oscillator, where

we showed that px = /2.

Slide 69

Outline (Contd.)

Orthogonality of Wavefunctions

Commutation of Operators

Differentiability and Completeness of the Wavefunctions

Dirac Bra-Ket Notation

Slide 70

35

Differentiability and Completeness

of the Wavefunction

Differentiability of

It is proven in in various texts** that the first derivative of the

wavefunction, d/dx, must be continuous.

because of the sudden change in the

derivative.

x

The one exception to the continuous derivative requirement is

if V(x).

We will see that this property is useful when setting Boundary

Conditions for a particle in a box with a finite potential barrier.

** e.g. Introduction to Quantum Mechanics in Chemistry, M. A. Ratner

and G. C. Schatz, Sect. 2.7

Slide 71

This means that any well behaved function defined over the

same interval (i.e. - to for a Harmonic Oscillator,

0 to a for a particle in a box, ...) can be written as a linear combination

of the eigenfunctions; i.e.

discuss approximate solutions of the Schrdinger equation for

multi-electron atoms and molecules.

Slide 72

36

Outline (Contd.)

Orthogonality of Wavefunctions

Commutation of Operators

Differentiability and Completeness of the Wavefunctions

Dirac Bra-Ket Notation

Slide 73

A standard shorthand notation, developed by Dirac, and termed

bra-ket notation, is commonly used in textbooks and

research articles.

In this notation:

of the integrand

of the integrand

Slide 74

37

In Bra-Ket notation, we have the following:

Scalar Product

of two functions:

Orthogonality:

Normalization:

Hermitian

Operators:

Expectation

Value:

Slide 75

38

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