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Physical Chemistry - 102: IISER Pune, Spring 2014 March 28, 2014

1. This document provides 10 problems related to physical chemistry concepts like operators, eigenfunctions, eigenvalues, and quantum mechanics. It asks the reader to express vectors in different bases, write equations in Dirac notation, prove properties of Hermitian operators, evaluate operators for different systems, and normalize wavefunctions. 2. Several questions ask the reader to prove properties of Hermitian operators, like real eigenvalues and orthogonal eigenfunctions. Other problems evaluate operators like position, momentum, and their variances for particle in a box and harmonic oscillator systems. 3. The document provides background information on operators, Dirac notation, and systems like particle in a box to help the reader understand and solve the 10 problems presented. It aims to build understanding

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Aakash Verma
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27 views2 pages

Physical Chemistry - 102: IISER Pune, Spring 2014 March 28, 2014

1. This document provides 10 problems related to physical chemistry concepts like operators, eigenfunctions, eigenvalues, and quantum mechanics. It asks the reader to express vectors in different bases, write equations in Dirac notation, prove properties of Hermitian operators, evaluate operators for different systems, and normalize wavefunctions. 2. Several questions ask the reader to prove properties of Hermitian operators, like real eigenvalues and orthogonal eigenfunctions. Other problems evaluate operators like position, momentum, and their variances for particle in a box and harmonic oscillator systems. 3. The document provides background information on operators, Dirac notation, and systems like particle in a box to help the reader understand and solve the 10 problems presented. It aims to build understanding

Uploaded by

Aakash Verma
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Physical Chemistry - 102

IISER Pune, Spring 2014


March 28, 2014
1. Given that a = 5

i -

j. Express a in terms of other basis and analyze the coecients ? (at
least two dierent basis which are linearly independent).
This question helps to you understand how same wavefunction can be expressed in dierent
basis. For example
| =
N

i=1
c
i
|
i
(1)
| =
N

i=1
c

i
_
(2)
where
i
and

i
are two linearly independent basis vectors and c
i
and c

i
are corresponding
coecients.
2. The equation

Af = g and its complex conjugate

A

= g

are written equivalently in Dirac


notation as

A|f = |g and f|

A

= g| respectively, where

A is an operator and f and g are
functions or vectors.

A

is called the adjoint of operator



A. Moreover the integral
_
f


Ag dx
is written in Dirac notation as
_
f

g
_
. A more general denition of a Hermitian operator
is
_


Af dx =
_

f

A

dx (3)
where f(x) and g(x) are two well behaved functions. Write the denition of Hermiticity (Eq.
(3)) in Dirac notation.
3. Hermitian operators are a special class of operators which are of particular importance in
quantum mechanics operators corresponding to quantum mechanical observables are Her-
mitian.
(a) Prove that the eigen values of an Hermitian operator are real.
(b) Show that the eigen functions
1
&
2
(non degenerate) of an Hermitian operator

A are
orthogonal to each other.
(c) Is momentum operator Hermitian? Momentum operator is dened as

P =

d
dx
(4)
4. (a) Show that cos (x), where is a constant, is an eigenfunction of the operator
d
2
dx
2
and
nd the eigenvalue.
(b) Show that e
(ikx)
are eigen functions of one dimensional momentum operator and nd
the eigen values.
5. In the following cases, nd

A

B and

B

A and comment on whether

A

B =

B

A
(a)

A f(x) = [f(x)]
2

B f(x) =
_
f(x)
1
(b)

A = x (i.e. multiply by x)

B =
d
dx
6. Expand the operator (
d
dx
+ x)
2
.
7. An Hermitian operator

A has eigenfunctions f
1
, f
2
, f
3
, ...., f
n
with corresponding eigen values
a
1
, a
2
, a
3
, ...., a
n
. The state of a system is described by a wavefunction given by
=
1
3
if
1

_
7
9
_
1/2
f
2
+
_
1
9
_
1/2
f
3
(5)
What are the probabilities of obtaining a
1
, a
2
and a
3
?
8. Consider a particle of mass m which is conned to a innite potential well box along the x
axis between x = 0 and x = a. For any stationary state wavefunction
n
(x) of this particle,
(a) Calculate the average value or expectation value of the position and momentum opera-
tors, i.e. calculate the following:


X =
_

n
(x)


n
(x)
_
(6)


P
x
=
_

n
(x)

P
x


n
(x)
_
(7)
(b) Calculate the variance of the position and momentum operators, i.e, calculate the fol-
lowing:

2
x
=
_

n
(x)

_

X

X
_
2

n
(x)
_
(8)

2
p
=
_

n
(x)

P
x


P
x

_
2

n
(x)
_
(9)
Note that a non-zero value of the variance indicates uncertainty in measurement, corre-
sponding to the fact that
n
(x) is not an eigenfunction of the position or momentum
operators. From the results, show Heisenberg inequality which states that
x

p
>

2
9. Evaluate the expectation vales of

X,

X
2
,

P
x
and

P
2
x
of the harmonic oscillator in ground
state.
10. Normalize the wavefunction
1s
(r, , ) = Ae
r/a
0
in the range r 0; 0 ; 0 2.
2

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