Chemical Bonding CHEM 6277-10 Lecture 2 Quantum Mechanical Principles Lecturer: Hanning Chen, Ph.D.

08/29/2013

Quiz 1 10 minutes

Please stop writing when the timer stops !

Quantum Mechanics Wavefunction

Wavefunction is the mathematical representation of a physical object. spatial and temporal distribution of a quantum state

( r, t ) r : position

t : time
* : complex conjugate

( r, t ) = a bi
*

i : imaginary unit

( r, t )

( r, t ) ( r, t ) = ( a bi ) ( a + bi ) = a + b
* 2

( r, t ) = ( r, t ) = ( r, t ) ( r, t )
2 *

can be a complex number

( r, t ) = a + bi

(r , t ) :

probability density

must be a non-negative real number

Information in a Wavefunction

( r, t )
Probability Density:

r : position
2

t : time

Wavefunction is the only quantity needed to represent a quantum state

( x)

( r, t ) = ( r, t ) = ( r, t ) ( r, t )
*

Spatial distribution higher probability

lower probability

What else information? How about momentum ?

Master Equation of Quantum Mechanics

Time-dependent Schrdinger Equation:

( x, t ) ( x, t ) i = + V x , t x , t ( ) ( ) 2 t 2m x
2 2

partial differential equation (x,t) two independent variables

Time-independent Schrdinger Equation:

d ( x) + V ( x ) x = E x ( ) ( ) 2 2 m dx
2 2

ordinary differential equation (x) one independent variable

n-th order linear ordinary differential equation

An ( x ) y

(n )

+ An 1 ( x ) y + ... + A1 ( x ) y + A0 ( x ) y = g( x ) n d y (0) 0 (n ) (n ) n for example y=y y =1 y = n, y y dx

'

( n 1)

Acceptable Wavefunctions
1. continuous 2. smooth

3. single-valued

( x)

( x)

NO!

NO!
( x)

NO!

x
4. square-integrable

x
2 2

NO!
x

( x)

( x) + V ( x ) x = E x ( ) ( ) 2 2 m x
The Schrdinger equation is a second-order partial derivative equation.

r , t r , t dr = 1 ( ) ( )
*

normalization rule

Solution of the Homogeneous Second-order ODE

generic form:

y + P ( x) y + Q( x) y = 0
'' '

Let us start with y1 ( x ) and y2 ( x ), both satisfying the generic form linear combination:

y = c1 y1 ( x ) + c2 y2 ( x )
' 1 1 ' 2 2

c y + c y + P ( x ) c y + P ( x ) c y + Q ( x ) c1 y1 + Q( x )c2 y2 = 0
'' 1 1 '' 2 2

0 0 An arbitrary linear combination of the solutions is also a solution

c1 y + P x y + Q x y + c y + P x y + Q ( x ) y = 0 ( ) ( ) ( ) 1 2 2
'' 1 ' 1 '' 2 ' 2

What is the Solution Form?

tentative solution: For

y1 = e , y2 = e
k1x

k2 x

y1

k e

2 k1x 1 2 1

+ Pk1e

k1x

+ Qe

k1x

=0

k + Pk1 + Q = 0
Well-known solutions:

(auxiliary quadratic equation)

2

P ( x ) P ( x ) 4Q ( x ) k1,2 ( x ) = 2

General solution of homogeneous second-order ODE:

y = c1e

k1x

+ c2 e

k2 x

Wavefunction of a Free Particle

Definition of a free particle:

V =0
2 2

V : potential

Time-independent Schrdinger equation:

( x) + V ( x ) x = E x ( ) ( ) 2 2 m x ( x) = E x ( ) 2 2m x
2 2

k E= 2m
2

Standard solution:

( x ) = c1e
*

ik1 x

+ c2 e

ik2 x

total energy, but also the kinetic energy

c1 , c2 : "arbitrary" constants

r , t r , t dr = 1 ( ) ( )

what is k?

Momentum of a Free Particle

If the free particle is treated by classical mechanics:

p Ek = E = p = 2 mEk 2m
kinetic energy given by Schrdinger equation:

p : momentum

k Ek = p = k 2m
2 2

( x ) = Ae + Be
ikx

ikx

the wavefunction does have the momentum information

Unfortunately, not every wavefunction can be easily expressed as a combination of plane waves Formal quantum mechanics definition of momentum: momentum operator

( x ) : arbitrary wavefunction
*

= i p x

( x ) dx p = ( x )p
expectation value

information extractor

Operator
function:

x = 1 f (x) = 2
A function has the magic to change the value of an independent variable.

f (x) = x + 1
2

x : indepedent variable

We define a rule, when

2

, so that d Df ( x ) = f (x) dx

f (x) = x + 1 if we define g( x ) = 2 x

d 2 Df ( x ) = ( x + 1) = 2 x dx Df ( x ) = 2 x = g( x )

An operator is a function of functions.

Important Properties of Operators

An operator acting on more than one function:

D ( f ( x, y), g( x, y)) = ( f ( x, y) + g( x, y)) + ( f ( x, y) + g( x, y)) x y

f ( x, y ) = x + y , g ( x, y ) = x + y
2 2

D( f ( x, y), g( x, y)) = 2 x + 2 y + 2 = h( x, y)
?

predefined mixture of functions Does the order of mixing matter ?

AB ( f ( x )) = BA ( f ( x ))

Commutator of Two Operators

Definition of Commutator:

[ A, B] = AB BA

If for any function f ( x )

difference between two mixing orders

[ A, B] f ( x ) = ABf ( x ) BAf ( x ) = 0
The operators of A and B are commute.
A simple example:

d d Af ( x ) = f ( x ), Bf ( x ) = 2 f ( x ) dx dx 2 2 3 3 d d d d d d [ A, B] f ( x ) = f ( x ) f ( x ) = f ( x ) f ( x ) = 0 2 2 3 3 dx dx dx dx dx dx

One More Example

d Af ( x ) = f ( x ), Bf ( x ) = xf ( x ) dx
do they commute? A is after B: B is after A:

d d ABf ( x ) = Bf ( x ) = ( xf ( x )) = xf '( x ) + f ( x ) dx dx d BAf ( x ) = x Af ( x ) = x f ( x ) = xf '( x ) dx

[ A, B] f ( x ) = ABf ( x ) BAf ( x ) = xf '( x ) + f ( x ) xf '( x ) = f ( x )

[ A, B] = 1 0

They DO NOT commute !

Why Does Commutator Matter?

momentum operator:

= i p x

position operator:

=x x

commutator of momentum and position operators:

, x ] ( x ) = p x ( x ) x p ( x ) = i ( x ( x )) xi ( ( x )) [p x x

, x ] ( x ) = i ( x ( x )) xi ( ( x )) = i ( x ) [p x x
momentum and position operators do NOT commute !
There is no way to simultaneously determine the momentum and position of a particle !

residue

Heinsberg Uncertainty Principle

Standard deviation:

A =

A A
2

: average value
2 2

Cauchy-Schwartz Inequality: For position and momentum,

A , B AB BA 2 2 2 2 A B A B 2 2

, x ] = i [p
2

2 p 2 x

, x ] [p 2

p x 4 2
2 2 p 2 x

For energy and time,

E t 2

It is impossible to exactly measure a particles energy at any given time.

Hamiltonian Operator
Time-independent Schrdinger equation:
2 2

a systems total energy

: Hamiltonian H operator

( x) + V ( x ) x = E x ( ) ( ) 2 2 m x

+ V ( x ) x = E x ( ) ( ) 2 2m x
2 2

Using the definition of momentum:

= i p x

p Ek = = 2 2m 2m x
2 2 2

H = Ek + V ( x )
kinetic energy potential energy

H ( x ) = E ( x )
eigenfunction-eigenvalue problem

Eigenfunction and Eigenvalues

Definitions:

D ( f ( x )) = cf ( x )

f ( x ) is the eigenfunction of the operator, D, and c is the eigenvalue for f ( x )

For a given operator, only some particular functions satisfy the condition. For a given eigenfunction, we only have one eigenvalue. A simple example:

d = D dx

f (x) = e f (x) = e

3x

2x

d 3x f ( x ) = 3e = 3 f ( x ) dx d 2x f ( x ) = 2e = 2 f ( x ) dx

Physical Meaning of Eigenfunction and Eigenvalue

The eigenfunction of an operator has a constant observable value, which is the eigenvalue. Time-independent Schrdinger equation:

H ( x ) = E ( x ) The eigenfunction ( x ) has a constant total energy

( x ) = Ae + Be
ikx ikx

E.

For a free particle:

= i YES Is it an eigenfunction of momentum ? p x ikx ikx ikx ikx ( x ) = i ( Ae + Be ) = (i )(ik ) ( Ae + Be ) = k ( x ) p x

A free particle has a well-defined momentum, Is it an eigenfunction of position ?

( x ) = x ( Ae + Be x
ikx

ikx

) = x ( x )

=x x

k , but not a well-defined position

x ( , + )
NO

Expectation Values
expectation value

A = ( x )A ( x ) dx
* *

average value of a physical observable, which is represented by an operator average total energy average momentum average position

E = ( x )H ( x ) dx ( x ) dx x = ( x )x
*

: Hamiltonian operator H

( x ) dx p = ( x )p
*

: momentum operator p : position operator x

Special case:
*

If

A ( x ) = a ( x )

eigenfunction-eigenvalue

* * A = ( x )A ( x ) dx = ( x )a ( x ) dx = a ( x ) ( x ) dx = a =1

Hermitian Operators
Hermiticity:

( x ) A x dx = ( ) j
* i

For example,
* i

=x x

A is a Hermitian operator
* *

( x ) A x dx ( ) i
* j

( a + bi )
* * j

= a bi
*

( ) ( (x)x ( x )dx ) Q.E.D. = ( ( x ) x ( x )dx ) = ( ( x ) x ( x )dx )

* ( x ) x x dx = ( x ) x x dx = ( ) ( ) j i j
i * j * * j * i i

If a physical property is observable, its corresponding operator must be Hermitian !

, x are all Hermitian operators because they are measurable. H, p

Hermicity of Quantum Operators

Let us say

is a Hermitian operator If A
*

A ( x ) = a ( x )
*

a : complex number a = f + gi

A = ( x )A ( x ) dx =
*

( ) x a x dx = x a x dx ( ) ( ) ( ) ( ) ( ) a ( x ) ( x ) dx = a ( ( x ) ( x ) dx )
x A x dx ( ) ( )
* * * *

a 1 = a (1)
*

a=a

a : real number

The Hermicity of quantum operators is used to ensure real observable values !

Superposition of Hermitian Eigenfunctions

A ( x ) = a ( x )
eigenfunction set: {1 ( x ), 2 ( x ),..., N ( x )} eigenvalue set: {a1, a2 ,..., aN } If A is a Hermitian operator

1 if i = j * x x dx = = ( ) ( ) i j ij 0 if i j spatial overlap between wavefunctions

normalization rule orthogonality

superimposed wavefunction

( x ) = ci i

linear combination

A = ( x )A ( x ) dx
*

i =1

Expectation Value for a Superimposed Wavefunction

( x) = c
* j =1 * j

A = ( x )A ( x ) dx
*
N * j

( x ) = ci i
N
i =1

A = c A ci i dx
j =1 * j * j i =1

ai dx = ai ij
* j i

A = c c A i dx
j =1 i =1 * j i * j

a dx i
* j i

A = c c a
j =1 i =1

* j i i ij

j=i

A = c c a
i =1

* i i i

A = ci ai
2 i =1

An Example
two-component decomposition:

1 and 2 are the eigenfunctions of Hamiltonian operator, H E1 and E2 are the corresponding eigenvalues

( x ) = c11 + c2 2

what is the expectation value of energy for ( x ) ?

E = c1 E1 + c2 E2
c1 and c2 : Projection of ( x ) onto 1 ( x ) and 2 ( x )
2 2

If ( x ) = 1 ( x ) c1 = 1 and c2 = 0
2 2

If ( x ) = 2 ( x )
2

c2 = 1 and c1 = 0

In general, 0< c1 < 1 and 0< c2 < 1

Review of Homework 1
1.11 A one-particle, one-dimensional system has the state function = ( sin at ) ( 2 / c
2 1/4

x 2 /c2

+ ( cos at ) ( 32 / c

6 1/4

xe

x 2 /c2

where a is a constant and c =2.0. If the particle's position is measured at t=0, estimate the probability that the result will lie between 2.000 and 2.001

t = 0 = ( 32 / c
2

6 1/4

( x ) = = ( 32 / c
x = 2.001 x = 2.000 x = 2.001

xe

x 2 /c2 2 2 x 2 /c 2

6 1/2

xe

P( x)

x = 2.000

32 / c ( )

6 1/2

xe

2 2 x 2 /c 2

dx = ( 32 / c

6 1/2

c 4

x x 2 /c2 erf ( ) c 2 xe c

x = 2.001 x = 2.000

c = 2.0 P( x)
x = 2.001 x = 2.000

0.000216

Homework 2

Reading assignment: Homework assignment:

Chapter 3 Problems 3.8 and 3.25

Homework assignments must be turned in by 5:00 PM, August 30th, Friday to my mailbox in the Department Main Office located at Room 107, Corcoran Hall