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Lecture 1: Classical Mechanics and the Schrdinger Equation This lecture covers the following parts of Atkins 1. Further information 4. Classical mechanics (pp 911- 914 ) 2. 11.3 The Schrdinger Equation (pp 294) Lecture-on-line Introduction to Classical mechanics and the Schrdinger equation (PowerPoint) Introduction to Classical mechanics and the Schrdinger equation (PDF) Handout.Lecture1 (PDF) Taylor Expansion (MS-WORD)

Tutorials on-line The postulates of quantum mechanics (This is the writeup for Dry-lab-II)( This lecture has covered (briefly) postulates 1-2)(You are not expected to understand even postulates 1 and 2 fully after this lecture) The Development of Classical Mechanics Experimental Background for Quantum mecahnics Early Development of Quantum mechanics The Schrdinger Equation The Time Independent Schrdinger Equation

Audio-Visuals on-line Quantum mechanics as the foundation of Chemistry (quick time movie ****, 6 MB) Why Quantum Mechanics (quick time movie from the Wilson page ****, 16 MB) Why Quantum Mechanics (PowerPoint version without animations) Slides from the text book (From the CD included in Atkins ,**)

Classical Mechanics

A particle in 3-D has the following attributes

mass

Position

m r 2. Position r

1. Mass

r
Y

velocit y

3. Velocity

r v

v = dr /dt
X

Rate of change of position with time

Expression for total energy

r The total energy of a particle with position r , r mass m and velocity v also has energy

ET

r Ekin Epot ( r )
Potential energy due to forces

Kinetic energy due to motion

The kinetic energy can be written as :

Ek

1 2 mv 2

Or alternatively in terms of the linear momentum:

r p
as:

v mv
Ek p 2m
2

p
v v small mass large velocity
or

v v
large mass small velocity

The potential energy and force

A particle moving in a potential energy field V is subject to a force

V(x)

F=-dV/dx

Force in direction of decreasing potential energy

Force in one dimension

dV ex dx

dV ey dy

Force F Potential energy V

The force has the direction of steepest descend

v F

r (dV / dx)ex

v v (dV / dy)e y (dV / dz)ez

v F

gradV

The Classical Hamiltonian

The expression for the total energy in terms of the potential energy and the kinetic energy given in terms of the linear momentum

p2 r E Ekin E pot V( r ) 2m is called the Hamiltonian H p2 r V( r ) 2m

The Hamiltonian will take on a special importance in the transformation from classical physics to quantum mechanics

Quantum Mechanics
We consider a particle of mass m,

r and position r r Linear momentum p

mass

r mv

Position m

r r
Y

r r p = mv
X Linear Momentum

The particle is moving in the potential V(x,y,z)

mass

Position m

r r
Y

r r p = mv
X Linear Momentum

The classical Hamiltonian is given by

1 2 px 2m

p2 y

p2 z

V(x, y, z)

1 r r p p 2m

v V( r )

1 2 p 2m

v V( r )

Quantum Mechanical Hamiltonian The quantum mechanical Hamiltonian H is constructed by the

following transformations :

HClass
x y z

Classical Mechanics Quantum Mechanics px py pz x y z x ; px y ; py z ; pz h i x h i y h i z

1 px 2 2m

p2 y

pz 2

V( x , y, z )

h Here h ' h - bar' = is a modification of Plancks constant h 2 h 1.05457 10 34 Js

1 ( px p 2 p z ) 2 y 2 2m 1 h h [( ) 2m i x i x

V( x , y, z) ( h i y h h ) ( i z i y h )] V(x, y, z) i z
2

We have

h i y
Thus

h i y

h2 i2 y
2

y
2

h2

y2

2 h2 [ 2 2m x

2]

V(x, y,z )

2 h2 [ 2 2m x

z
2

2]
2

V(x, y,z )
2 2

By introducing the Laplacian : 2 2 2 we have x y z h 2 V(x, y, z) H 2m It is now a postulate of quantum mechanics that : the solutions (x, y, z) to the Schrdinger equation

H (x, y, z) h2 2m
2

E (x, y, z) r E (r ) E

r r r ( r ) V( r ) ( r )
2 2 2

h2 2 [ 2 2m x

] V(x, y, z)

Contains all kinetic information about a particle moving in the Potential V(x,y,z)

What you should learn from this lecture

Definition of : Linear momentum (pm), p2 kinetic energy( ); 2m Potential Energy
Relation between force F r r and potential energy V F = - V) (

The definition of the Hamiltonian (H) as the sum of kinetic and potential energy, with the potential energy written in terms of the linear momentum

For single particle: H

r p2 V( r ) 2m

 You must know that : The quantum mechanical Hamiltonian H is constructed from the classical Hamiltonian H by the transformation

HClass

1 px 2 2m
x y z

p2 y

pz 2

V( x , y, z )
h i x h i y h i z

Classical Mechanics Quantum Mechanics x y z px py pz x ; px y ; py z ; pz

Appendix A Newton' s Equation and determination of position..cont

The position of the particle is a function of time. Let us assume that the particle at has the position and the velocity What is

t
to

r r v(t o ) (dr / dt)t

r r (to )

to
v (d r / dt )t tot v (d 2 r / dt2 )t v + r(to t)
to

t2

r By Taylor expansion around r (to )

v r (t o v v t) = r ( to ) + (d r / dt) t
to

v r (to

v t) = r (t1 ) = ?

v r (t o )

v r (t o

or

1 2v t + (d r / dt 2 ) t 2
to

to

t2

v 1 2v v 2 t) = r (t o ) + v(to ) t + (d r / dt )t 2

Appendix A Newton' s Equation and determination of position..cont

v r (t o

v 1 2v v 2 t) = r (t o ) + v(to ) t + (d r / dt )t 2

to

v v (t o ) t v r (t o )

(d r / dt )t v + r (t o t)

2v

to

t 2

Thus :

v F(to )

However from Newtons law:

gradV

m(d r / dt 2 ) t

2v

to

v r (t o

v 1 v 2 t) = r (t o ) + v(to ) t (gradV)t=t 0 t 2m

Newton' s Equation and determination of position..cont

v r (t o

v 1 v 2 t) = r (t o ) + v(to ) t (gradV)t=t 0 t 2m

v v(t o ) t v r (t o )

1 t - (gradV)t = to m v + r (t o t)

Appendix A Newton' s Equation and determination of position..cont

At the later time :

v r(t 1

v v t) = r(t 1 ) +(dr / dt)t

t1

to

t
t1

we have

1 2v t + (d r / dt 2 )t 2

t1

t 2 (1)

v F(t1 )
as

The last term on the right hand side of eq(1) can again be determined from Newtons equation

gradV

m(d r / dt ) t

2v

t1

(d r / dt )t

2v

t1

1 (gradV)t m

t1

Appendix A Newton' s Equation and determination of position..cont

v r(t 1

v v t) = r(t 1 ) + (dr / dt)t

t1

1 t+ (gradV) t 2m

t1

t 2 (1 )

We can determine the first term on the right side of eq(1) By a Taylor expansion of the velocity

v (dr / dt)t
or

t1

v (dr / dt)t

t0

1 2v (d r / dt 2 )t 2
to
to

t0

v (dr / dt)t

t1

v v(t o )

Where both:

v v(t o )

1 (gradV) t 2m
1 (gradV)t and m

t
are known

v At t 2 t 0 2 t what about r(t 2 t) ? 1 2v v v v t) = r(t 2 ) + v(t 2 ) t + (d r / dt 2 ) t t 2 t 2 r(t 2 2 1 v v v (gradV) t t 1 t v(t 2 ) (dr / dt)t t 2 v(t 1 ) m 1 2 2v (d r / dt ) t t 2 (gradV)t t 2 m
v(t 2 ) t r (t 2 ) 1 - (gradV) t m t= t2 r(t2 t)

Appendix A Newton' s Equation and determination of position..cont

The position of a particle is determined at all times from the position and velocity at to