CHAPTER 1

INTRODUCTION TO QUANTUM MECHANICS

HISTORICAL BACKGROUND

1801- T.Young gave experimental evidence for the wave nature of light.

1860- J. C. Maxwell predicted that an accelerated electric charge would radiate energy in the form
of electromagnetic waves consisting of oscillating electric and magnetic fields.

1888- Hertz confirmed Maxwell's equations.

1900- Max Planck developed a theory in excellent agreement with the observed blackbody
radiation curves.The assumption was that the atoms of the blackbody could emit light of energy in
-34
amounts given by h (h=6.62*10 J. s).

1905 -Einstein showed that light is composed of particlelike entities called photons with each
photon having an energy
E=h
When an electron in the metal absorbs a photon, part of the absorbed photon energy is used to
overcome the forces holding the electron in the metal and the rest appears as the kinetic energy of
the electron after it has left the metal.
An increase in light intensity at fixed frequency increases the rate at which photons strike the
metal and increases the rate of emission of electrons but does not change the kinetic energy of
each emitted electron.(check photoelectric effect experiment!!)

STRUCTURE OF MATTER

Towards the end of the nineteenth century electrons were known to be negative charges.Protons
were identifed as positive charges which were 1836 times as heavy as the electrons.

In 1932 Chadwick discovered the neutron.

In 1894-1897 J. J.Thomson measured the e/m ratio for the electron.

(check experiment!)

In 1906-1914 Millilkan measured the charge (e) of the electron using the oil drop experiment.
(check it!)

In 1909 Rutherford proved that the positive charge is concentrated in the nucleus.
In 1911 Rutherford proposed the planatery model for the atom. The electrons in Rutherford
model should loose their energy by radiation and would spiral towards the nucleus.
According to classical physics Rutherford atom is unstable and would
collapse.(check experiment!)

In 1913 Bohr assumed that the electron in a hydrogen atom can move only on one of a number of
allowed circles.He obtained good agreement with hydrogen spectrum.The theory could not
account for chemical bonds in molecules.(check experiment)

In 1923 Louis de Broglie suggested that the motion of electrons might have a wave aspect.The
2
energy of any particle can be expressed as E=mc
2
where c is the speed of light and m is the mass of the particle .Using E=h we get mc = h = hc/
and  =h/mc=h/p.

Although photons and electrons show a duality, they are not the same kind of entities. Photons
travel at speed c and have zero rest mass; electrons have v<c and have a nonzero mass.

THE TIME DEPENDENT SCHRODINGER EQUATION

Classical mechanics applies to macroscopic particles.For microscopic particles quantum

mechanics are required. Heisenberg uncertainty principle shows that we cannot determine
simultaneously the exact position and velocity of a microscopic particle.In quantum mechanics we
cannot predict the exact future motion.
The approach in quantum mechanics is to postulate the basic principles and use these postulates
to deduce experimentally testable consequences such as the energy levels of the atoms.The state
of a system is described by postulating a wave function or state function . Since the state
changes with time,  is a function of time.
For a one particle, one dimensional system the equation is postulated to be

-h/i(∂(x,t)/∂t)=-(ħ2/2m)(∂2(x,t)/∂x2+V(x,t)(x,t))

where the constant ħ is defined as

ħ=h/2p

this equation was discovered in 1926 by the Austrian physicist E.Schrödinger(1887-1961).In this
equation ,known as the time dependent Schrödinger equation ,i=√-1,m is the mass of the particle
and V(x,t) is the potential energy function of the system.
Born postulated that

(x,t)2 dx

gives the probability at time t of finding the particle in the region of the x axis lying between x
and x+dx.The function (x,t)2 dx is the probability density for finding the particle at various
places on the x axis.
Quantum mechanics is statistical in nature.Knowing the state we cannot predict the probabilities
of various possible results. Bohr’s theory of the hydrogen atom specified the precise path of the
electron and is therefore not a correct quantum-mechanical picture.
Quantum mechanics was first formulated in 1925 by Heisenberg, Born and Jordan using matrices
several months before Schrödinger's 1926 formulation.

THE TIME INDEPENDENT SCHRÖDINGER EQUATION

For many applications of quantum mechanics in chemistry it is not necessary to deal with the
time dependent wave equation; instead the time independent Schrödinger equation is used.
Restrict yourself to the case where the potential energy is not a function of time but depends only
on x.
The time dependent Schrödinger equation is

2 2 2
-ħ/i(∂(x,t)/dt)=(-ħ /2m)(∂ (x,t)/∂x +V(x)(x,t))

Now look for solutions that can be written as the product of a function of time and a function of
x:

(x,t)=f(t)y(x)

∂(x,t)/∂t=df(t)/dt y(x)

2 2 2 2
∂ (x,t)/∂x =f(t) d y(x)/dx

and

2 2 2
(-ħ/i)(df(t)/dt)(x)=(- ħ /2m )(f(t)) (d y(x)/dx +V(x)y(x))

The separation of variables gives

(- ħ /i)(1/f(t))df(t)/dt=(-h2/2m)[(1/ )(d2y(x)/dx2 +V(x)]

df(t)/f(t)=(-iE/h)dt

integrating both sides of this equation with respect to t we have

ln f(t)=-iEt/h+C

where C is an arbitrary constant of integration.

Hence

f(t)=Ae-iEt/h
The equation
-ħ2/2m(d2(x)/dx2 +V(x) (x)=E(x)

is the time independent Schrodinger equation for a single particle of mass m moving in one
dimension.

For the case where the potential energy is a function of x only

(x,t)=e-iEt/ħ y(x)

States of the form of the above equation are called stationary states.,where stationary stands for
the probability density and doesn’t mean that the particle is at rest.

PROBABILITY

If an experiment has n equally probable outcomes ,m of which are favorable to the occurence of a
certain event A then the probability that A occurs is m/n.
In quantum mechanics the probabilities involve a continious variable.We talk of the probability of
finding the particle between x and x+dx.The probabililty that the particle will be found between x
and x+dx is equal to g(x)dx where g(x) is called the probability density.Quantum mechanics
2
postulates that the probability density is given by  .The probability that the particle lies in some
finite region of space a<x<b is given by

2


Since it is certain that the particle is somewhere on the x axis there is the requirement that

2
 dx = 1

When  satisfies the above equation it is said to be normalized.

OPERATORS

The one-particle,one-dimensional time independent Schrödinger equation can be written in the

form

(-ħ2/2m)[(d2/dx2)+V(x)](x)=E(x)

The entity in brackets is an operator.The energy operator operating on the wave function gives us
the wave function back again multiplied by the allowed values of the energy.
The operator is a rule that tranforms a given function into another function.
The sum and difference of two operators  and Ĉ are defined by the equations
(Â+Ĉ)f(x)=Âf(x)+Ĉf(x)

(Â-Ĉ)f(x)=Âf(x)-Ĉf(x)

The commutator [Â,Ĉ] of the operators  and Ĉ is defined as the operator

ÂĈ-ĈÂ:

[Â,Ĉ]=ÂĈ-ĈÂ

The square of an operator is defined as the product of the operator with

itself:

Â2=Â.Â.

A is a linear operator if and only if it has the following properties:

 [f(x)+g(x)]=Âf(x)+Âg(x)

 [cf(x)]=cÂf(x)

where f and g are arbìtrary functions and c is an arbitrary constant.

Hermitian operators

Let A be the linear operator representing the physical property A.The average value of A is

<A>= *Âdt

where  is the state fuction of the system.Since the average value of a physical quantity must be
a real number

<A>=<A>*

*Âdt = (Â)*dt

A linear operator that satisfies the above equation for all well behaved functions is called a
Hermitian operator.

EIGENFUNCTIONS AND EIGENVALUES

Suppose that the effect of operating on some function f(x) with the operator A is to multiply f(x)
by a certain constant k. Then f(x) is an eigenfunction of A with eigenvalue k.

THE ONE - DIMENSIONAL PARTICLE IN A BOX

The free particle travelling in one dimension has the Hamiltonian

2 2 2
Ĥ=-(ħ /2m)(d /dx ) (NO POTENTIAL!)

The time independent Scrödinger equation can be written as

Ĥ=E

2 2 2
-( ħ /2m)(d /dx )=E

The solutions to this equation are

ikx -ikx
(x) =Ae +Be

2 0.5
with k=(2mE/ ħ )

An alternative solution to this equation is

(x)= Ccoskx + Dsinkx

At x=0 (0)=0 thus C=0

At x=L (L)=0 thus Dsin(kL)=0

so either D=0 or sin(kL)=0

D cannot be zero, which implies that kl=nπ

k=nπ/L n=1,2,3

2 2 2
En=n (h /8mL )

The only problem is to determine D and this can be done using the normalization (or total
probability criteria)

2 2 0.5
D sin (nπx/L)dx =1 thus D= (2/L)

The solution for the motion of the free particle in a one dimensional box becomes

0.5
 n=(2/L) sin(nπx/L)

2 2 2
En=n (h /8mL ) n=1,2 etc
THE PARTICLE IN A THREE DIMENSIONAL BOX

There are many possible shapes for a three-dimensional box.The box considered is a rectangular
parallelepiped with edges of length a,b,c.Within the box ,the potential energy is zero, outside the
box it is infinite:

V(x,y,z)=0 in the region 0<x<a, 0<y<b, 0<z<c (38)

V=∞ elsewhere (39)

Since the probability for the particle to have infinite energy is zero, the wave function must be
zero outside the box.Within the box, the potential energy operator is zero and the Schrödinger
equation is

2 2 2 2 2 2 2
(-ħ /2m)(∂ /∂x +∂ /∂y +∂ /∂z ) = E (40)

Asume that the solution to (40) can be written as Y(x,y,z)=f(x)g(y)h(z)

The method is called separation of variables.

0.5 2 2 2
f(x)=(2/a) sin(n πx/a) E =n h /8ma n =1,2,3 etc (41)
x x x

0.5 2 2 2
g(y)=(2/b) sin(n πy/b) E =n h /8mb n =1,2,3 etc (42)
y y y

0.5 2 2 2
h(z)=(2/c) sin(n πz/c) E =n h /8mc n =1,2,3 etc (43)
z z z

2 2 2 2 2 2 2
E=(h /8m)(n x/a +n y/b +n z/c ) (44)

0.5
(x,y,z)=(8/abc) sin(n πx/a) sin(n πx/b) sin(n πx/c) (45)
x y z

States with different quantum numbers may have the same energy:
the states  , , (where the subscripts give the quantum numbers) all have the same
211 121 112
energy. When two or more independent wave functions correspond to states with the same energy
eigenvalue ,the eigenvalue is said to be degenerate. The degree of degeneracy of an energy level
is the number of states that have that energy. It is also equal to the number of linearly independent
wave functions corresponding to that value of the energy. Thus the second-lowest energy level of
the particle in a cube is threefold degenerate.

AVERAGE VALUES
The average value of B is defined as the arithmetic mean of the observed values b1,b2,.....bn

<B>= bj/N

where N, the number of systems,is extremely large.Instead of summing over the observed values
of B we can sum over all possible values of B,multiplying possible value by the number of times it
is observed

<B>= n b/N
b

where n is the number of times the value b is observed.

b

Example: Suppose a class of nine students takes a quiz and that the students receive these
grades:0,20,20,60,60,80,80,100.

Calculating the average grade ,we have

1/N  b =(0+20+20+60+60+80+80+80+100)/9=56
j

The average grade will be calculated according to

1/N  nbb = (1(0)+2(20)+0(40)+2(60)+3(80)+1(100))/9=56

The above equation can be rewritten as

<B>=  (n /N)b
b

since N is extremely large, n /N is the probability P of of observing the value b and

b b

<B>=  P b
b
The average value of the x coordinate for a one particle, one dimensional system in the state
(x,t) can be calculated as

2
<x>= x dx

The term expectation value is often used instead of average value.

REQUIREMENTS FOR AN ACCEPTABLE WAVE FUNCTiON

A function meeting these requirements is said to be well behaved.

- The function must be continious

- must be quadratically integrable
- must be single valued.
-The partial derivatives ∂/∂x,∂/∂y ,∂/∂z must be continious

POSTULATES OF QUANTUM MECHANICS

Postulate 1. The state of a system is described by a function  of the coordinate and the time.This
function,called the state function or wave function,contains all the information that can be
determined about the system. is single valued,continious and quadratically integrable

Postulate 2. To every physical observable there corresponds a linear Hermitian operator.To find
this operator ,write down the classical-mechanical expression for the observable in terms of
Cartesian coordinates and corresponding linear-momentum components, and then replace each
coordinate x by the operator x and each momentum component p by the operator -iħ∂/∂x.
x

Postulate 3. The only possible values that can result from measurements of the physically
observable property  are the eigenvales b in the equation Âg =b g where  is the operator
i i i i
corresponding to the property b . The eigenfunctions are required to be well behaved.
i

Postulate 4. If  is any linear Hermitian operator that represents a physically observable

property,then the eigenfunctions g of  form a complete set.
i

Postulate 5. If (q,t) is the normalized state function of a system at time t, then the average value
of the physical observable  at time t is

<A>= *Âdt

Postulate 6. The time development of the state of an undisturbed quantum-mechanical system is

given by the Schrödinger time-dependent equation

(-ħ/i)(d/dt)=Ĥ

where Ĥ is the Hamìltonian operator of the system.