Page 1

Quantum Mechanics
Lecture-6
Reference: Concept of Modern Physics
by A. Beiser
Page 2
An equation for matter waves?
De Broglie postulated that every particles has an associated wave of wavelength:
p h/ =
Wave nature of matter confirmed by electron diffraction studies etc (see earlier).
If matter has wave-like properties then there must be a mathematical function that is the
solution to a differential equation that describes electrons, atoms and molecules.
The differential equation is called the Schrdinger equation and its solution is called the
wavefunction, +.
What is the form of the Schrdinger equation ?
Page 3
1. Time Dependent Schrdinger Wave equation
2 2
2
(x, t)
i V (x, t)
t 2m x
| | c+ c
= + +
|
c c
\ .

E H + = +
2
2
i V
t 2m
( c+
= V + +
(
c

+ V =
c
+ c
2
2
2
m t
i

Hence

In 3D form

For free particle V = 0

This equation is called as time dependent form of Schrdinger wave equation for a material
particle in non-relativistic motion.
Page 4
2. Time independent or steady state form of Schrdinger wave equation
( )
2
2 2
2m
E V 0
x
c +
+ =
c
( )
2
2
2m
E V 0 V + + =
0
2
2
2
= + + V E
m

In 3D form

For free particle U = 0

Points of note:
1. The TDSE is one of the postulates of quantum mechanics. Though the SE cannot be
derived, it has been shown to be consistent with all experiments.
2. SE is first order with respect to time (cf. classical wave equation).
3. SE involves the complex number i and so its solutions are essentially complex. This is
different from classical waves where complex numbers are used simply for
convenience.
** All Prelims problems are concerned with solving TISE rather than the TDSE!
The TISE can often be very difficult to solve it depends upon V(x)!
Page 5
If particles have a wave description then they should obey a wave
equation
A wave equation has a general form,
1
(r,t) =
2
(r,t)
where
1
and
2
are operators associated with r and t respectively.
1D wave with a particular k-vector and frequency will have the
form
k,e
(x,t)=Asin(kx-et).
-
1

k,e
(x,t)=f (k)Asin(kx-et)
-
2

k,e
(x,t)=g(e)Asin(kx-et)
- Here f (k) and g(e) are eigen values of the respective operators.
For specific boundary conditions only specific values of k and e,
i. e. k
n
and e
n
, satisfy the boundary conditions
Operators, Eigenfunctions and eigenvalues

f(x)=a f(x)
Page 6
Classical Wave Operators
2
2
2 2
2
) , ( 1 ) , (
t
t x E
v x
t x E
c
c
=
c
c
Between perfectly reflecting walls have solutions for the wave equations:


Solutions satisfying the boundary conditions, E(x=0,a) = 0 require,
sin(ka) = 0. This gives, k
n
a = nt or k
n
= nt/a and e
n
= ck
n
= cnt/a, n = 1,2,3
We may say then that the wave, E(x,t) above is a solution of the wave
equation and that the eigenfunctions of the wave equation are






t kx A t kx A t kx A t x E e e e cos sin 2 ) sin( ) sin( ) , ( = + + =
t x k A t x E
n n n
e cos sin 2 ) , ( =
2
2
n
2
E(x, t)
k E(x, t)
x
c
=
c
2 2
n
2 2 2
1 E(x, t)
E(x, t)
v t v
e c
=
c
-k
n
2
=-e
n
2
/v
2
Consider the wave equation for light


For a traveling wave, solutions of the eigenfunctions Asin(kx-et),
are set of eigen values, called eigen vectors. Eigenvalues of the operator
on the left hand side are -k
n
2
eigenvalues of the operator on the
right hand side are -e
n
2
/v
2

For a standing wave between two reflecting mirros separated by a
distance a, the eigenvalues are, -k
n
2
= n
2
t
2
/a
2
Page 7
An operator is an instruction, a symbol which tells us to perform one or more
mathematical acts on a function, say f(x). The essential point is that they act on a
function.
Operators act on everything to the right, unless the action is constrained by brackets.
Addition and subtraction rule for operators:
( ) ) ( ) ( ) (
2 1 2 1
x f Q x f Q x f Q Q

=
The product of two operators implies succesive operation:
| | ) ( ) (
2 1 2 1
x f Q Q x f Q Q

=
The product of two operators is a third operator:
2 1 3
Q Q Q

=
Two operators commute if they obey the simple operator expression:
| |
1
2 2 1 1 2 2 1 2 1
0 , Q Q Q Q Q Q Q Q Q Q

= = =
- More on Operators -
Page 8
Example: function sin 2x

operator

eigenvalue ?

Solution:

eigenvalue
Note: In Quantum mechanics, the allowed eigenfunction
1. must be finite for all x
2. must be single-valued for all x
3. must be continuous for all x

2
2
d
dx

2
2
d
(sin2x) 4(sin2x)
dx
=
Page 10
2
p
E = V
2m
+
Physical Quantity(observable) Operators
symbol actual operation
Quantum Mechanical Operators
2 2
2 2
ih 1 h
- V
2 t 2m 4 x
c c
= +
t c t c

Page 11
Physical Quantity(observable) Operators
symbol actual operation
Quantum Mechanical Operators
x x
2 2 2
2
Position x x x

Linear Momentum p p i
x

Momentum in 3D p p i

Total Energy E E i
t

Kinetic Energy KE
2m 2m x
Potentail

c

c
V
c

c
c

c
2

Energy U(x) U(x) U(x)

Total Energy H H [ V]
2m
(Hamiltonian form)

+
Page 12
Expectation Values
Only average values of physical quantities can be determined (cant
determine value of a quantity at a point)
These average values are called Expectation Values
These are values of physical quantities that quantum mechanics
predicts and which, from experimental point of view, are averages
of multiple measurements
Example, [expected] position of the particle


Since P(r,t)dV=|(r,t)|
2
dV, we have a way to calculate expectation values if
the wavefunction for the system (or particle) is known

xP(x)dx
x , with P(x)dx 1
P(x)dx
+
+

= =
}
}
}
2 2
*
*
xP(x, t)dx
x x (x, t) dx, since (x, t) (x, t) (x, t)
P(x, t)dx
x (x, t)x (x, t)dx
+
+

= = + + = + +
= + +
}
}
}
}
Page 13
Expectation Value for Momentum of a Free Particle
Generally



Free
Particle
| |
* *
*
*

(x) p (x) dx (x) i (x) dx

x
p
1
(x) (x)dx
(x)
p i (x) dx
x
+ +

+

c (
| |

|
(
c
\ .

= =

c
=
c
} }
}
}
| | | |
| |
| | | | | | | | p k dx Ae Ae k dx Ae ik
i
Ae p
dx Ae
x i
Ae p
A
dx Ae Ae dx x Ae x
ikx ikx ikx ikx
ikx ikx
ikx ikx ikx
= = = =
(

c
c
=

= = =
} }
}
} }
+

+

+

+

+

* *
*
* 2
n integratio of limits as 0 where
, 1 ) ( with ) (
Page 14
Exercise: Determine < x > for a particle in a box of length L.










n
L
n n
0
L
2
0
2
2 n x
(x) sin
L L
x (x) * x (x)dx
2 n x
xsin dx
L L
2 L L
L 4 2
t
=
< >=
t
=
= =
}
}
L L
0 0
L
2
2
0
L
2 2 2
0
2 n nkx nkx
p *(x) (x)dx sin cos dx
i x i L L L L
2 1
k sin(kx) cos(kx)dx 0 (sin ce sin ax cos ax dx sin ax)
L i 2a
nkx
p sin 0 (sin 0 sin n 0, n 1, 2, 3,....)
iL L
c t
< >= + + =
c
= = =
(
< >= = = t = =
(

} }
} }
n
2 n x
(x) sin
L L
t
=
Exercise: Determine < p > for a particle in a box of length L.
Page 15
Exercise: A Particle limited to the x-axis has the wave
function =ax between x=0 and x=1; =0 elsewhere.

(a)Find the probability that the particle can be found x=0.45
and x=0.55.

(b)Find the expectation value < x > of the particles position.



(a) 0.0251 a
2

(b) a
2
/4
Page 18
*
2 1
*
1 2
1 2
Condition for orthogonal wavefunction
d 0
or d 0
wavefunction and are mutually orthogonal

t =
t =

}
}
* *
1 1 2 2
1 2
Condition of normalized wavefunction
d 1 or d 1
and called normalized wavefunction.

t = t =

} }
*
i j
Condition of orthonormal function
d 0 if i j
= 1 if i = j

t = =
}