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QUANTUM Mechanics PDF
QUANTUM Mechanics PDF
Chapter 2
Example 2: A ball bounces back off earth. You are asked to solve this quantum mechanically assuming the
earth is an infinitely hard sphere. Consider surface of earth as the origin implying V 0 and a linear
potential eleswhere (i.e. V x mgx for x 0 ). Which of the following wave function is physically admis-
sible for this problem (with k > 0):
e kx kx 2 2
(a) x (b) x Ae (c) x Axe kx (d) x Axe kx
x
Concept of wave function 25
Soln. Since the earth has been taken as infinitely hard sphere, therefore the wave function of the ball will be zero for
x < 0, non-zero for x > 0 and zero at infinity.
Since x should be continous everywhere, the wavefunction of the ball will be zero at x = 0.
Correct option is (d).
2.2 Physical significance of wave function :
Generally, x, t is a complex quantity. It can be multipliedd by any complex number without affecting its
physical significance. In general, x, t has no direct physical significance. But the quantity
2
* x, t x , t x , t is real, physically significant and is defined as position probability density i.e.
probability of finding the particle per unit length at time ‘t’. Therefore, for 1-D motion the probability of
finding the particle between x to x + dx at time ‘t’ is given by
2
* x, t x, t dx x , t dx
and for 3-D motion the probability of finding the particle within the volume element d located between
r and r dr at time ‘t’ is given by
2
* r , t r , t d r , t d
Now, x, t or r , t should be chosen such that total probability of finding the particle in the entire
space should be equal to unity i.e.
* 2
x, t r , t d x, t d 1 (for 1-D motion)
* 2
r , t r , t d r , t d 1 (for 3-D motion)
all all
space space
* 2 *
x, t x, t dx N x, t x, t dx 1
1
N
*
x, t x, t dx
Example 3: Normalize the wave function given by
x Ne x x 0
Ne x x 0
26 Concept of wave function
Soln. Normalization condition is
0
2 2 x
*
dx 1 N e dx e 2 x dx 1
0
2 1 1
N 1 N
2 2
Orthogonality condition of wave functions :
Two wavefunctions m x and n x are said to be orthogonal to each other, if
*
m x n x dx 0 m n
i.e. if a particle is in the state m x , then the particle cannot be in the state n x simultaneously together..
(ii) Two functions i x and j x are said to be orthogonal if their inner product is zero i.e.
b
i j i* x j x dx 0
a
This is known as orthogonality condition of two wave functions.
(iii) The norm of a function i x is defined as
1/ 2
b
N i i i * x i x dx
a
(iv) A function is said to be normalized if the norm of the function is unity i.e.
1/2
b
N i i i* x i x dx 1
a
This is known as normalization condition of a particular wave functions.
Concept of wave function 27
(v) Functions which are orthogonal and normalized are called orthonormal functions and they will satisfy the
condition:
b
i j i* x j x dx ij
a
(vi) A set of functions 1 x , 2 x , 3 x ........ is linearly independent if there exist a relation like
c1 1 x c2 2 x c3 3 x ................ 0 , where all c1 , c2 , c3 .......... are zero. Otherwise, they are
said to be linearly dependent. A set of linearly independent functions is complete.
Position Operator : xˆ , yˆ , zˆ
Momentum Operator : pˆ x i , pˆ y i , pˆ z i pˆ i
x y z
Potential energy Operator : Vˆ
ˆ pˆ 2 2 2
Kinetic energy Operator : K
2m 2m
Commutator Bracket:
The commutator bracket of two operators Aˆ and Bˆ is defined as Aˆ , Bˆ AB
ˆ ˆ BA
ˆˆ.
Example:
d d d d d d
(1) xˆ , xˆ xˆ x x xˆ, 1
dx dx dx dx dx dx
ˆˆ x pˆ x xˆ ix
(2) xˆ , pˆ x xp i x i xˆ , pˆ x i
x x
Similarly, yˆ , pˆ y i and zˆ, pˆ z i
Linear Operator:
If an operator  is said to be a linear if
(i) Aˆ c x cAˆ x and (ii) Aˆ 1 x 2 x Aˆ 1 x Aˆ 2 x
All Quantum mechanical Operators are linear in nature.
Properties of the commutator bracket:
1. Aˆ , Bˆ Bˆ , Aˆ 2. Aˆ , Bˆ Cˆ Dˆ .... Aˆ , Bˆ Aˆ , Cˆ ........
28 Concept of wave function
†
3. Aˆ , Bˆ Bˆ † , Aˆ † 4. Aˆ , BC
ˆ ˆ Aˆ , Bˆ Cˆ Bˆ Aˆ , Cˆ
5. Aˆ , BC
ˆ ˆ Bˆ , Cˆ , Aˆ Cˆ , Aˆ , Bˆ 0
6. Aˆ , f Aˆ 0
7. f Aˆ , G Aˆ 0
8. f Aˆ , G Bˆ 0 only if Aˆ , Bˆ 0
9. Aˆ , Bˆ nBˆ Aˆ , Bˆ 10. Aˆ , Bˆ nAˆ Aˆ , Bˆ
n n 1 n n 1
Soln: Aˆ , Bˆ , Bˆ , Aˆ Aˆ , Bˆ Bˆ , Aˆ Bˆ , Aˆ Aˆ , Bˆ
= AB ˆ ˆ BA
ˆ ˆ BA
ˆ ˆ AB
ˆ ˆ BA
ˆ ˆ AB ˆ ˆ AB
ˆ ˆ BA
ˆˆ
ˆ ˆ ˆ ˆ ABAB
= ABBA ˆ ˆ ˆ ˆ BABA
ˆ ˆ ˆ ˆ BAAB
ˆ ˆ ˆ ˆ BAAB
ˆ ˆ ˆ ˆ ABAB
ˆ ˆ ˆ ˆ BABA
ˆ ˆ ˆ ˆ ABBA
ˆ ˆ ˆˆ 0
Soln: x 2 , p 2 x 2 , pp x 2 , p p p x 2 , p 2 x x, p p p 2 x x , p 2i xp px
p2
Example 6: If ˆ
H V x , then calculate x, x, Hˆ .
2m
x, Hˆ x, p x,V x 1 x, p 2 0 1 2 p x, p i p
2
Soln:
2m 2m 2m m
x, x, Hˆ x, i i 2
m p x, p
m m
If the commutator bracket of two operators A ˆ and Bˆ is equal to zero i.e. Aˆ , Bˆ 0 , then the physical
observables corresponding to these operators are simultaneously accurately measurable and they have a com-
plete set of simultaneous eigenfunctions.
d
Example 7: The operator x has the eigenvalue . Determine the corresponding wavefunction.
dx
d d d
Soln: Eigenvalue equation: x x x dx
dx dx
Concept of wave function 29
x2 x2
ln x ln 0 0 exp x
2 2
ax2
d2 2
Example 8: Find the constant B which makes e an eigenfunction of the operator 2 Bx .
dx
What is the corresponding eigenvalue?
d2 2 2
Soln: 2 Bx 2 e ax 4a 2 x 2 2a Bx 2 e ax
dx
2 d2
For e ax to be eigenfunction of the operator 2 Bx 2 , then the eigenvalue
dx
4a x
2 2
2
2a Bx 2 must be independent of x i.e. 4a B 0 B 4a
2
d2 2 ax2 2
Therefore, 2 Bx e 2ae ax ; Thus the eigenvalue of the operator is (-2a).
dx
Hermitian operator:
A operator  is said to be hermitian if Aˆ † Aˆ and its should satisfy the following relation:
†
Dirac representation: Aˆ Aˆ †
Aˆ
*
Schrodinger representation: , Aˆ Aˆ , * Aˆ d Aˆ d
Properties:
(1) Eigenvalues of hermitian operators are real.
(2) Eigenfunctions corresponding to different eigenvalues of a hermitian operator are orthogonal.
(3) All physical observable in quantum mechanics are represented by hermitian operators.
Example: , pˆ x * i dx * i
dx
x
x
* *
d d
i * i dx i dx pˆ *x * dx
dx
dx
bˆ†bb
ˆ ˆ†bˆ 2
bˆ† 1 bˆ†bˆ bˆ 2
bˆ†bˆ bˆ†bˆ†bb
ˆ ˆ 2 bˆ †bˆ 2 2 0, 1
2 2
Example 10: Let the wave function of a particle of mass ‘m’ at a given instant be x Ae x / a .
What will be the function K x where ‘K’ is the kinetic energy? Is this wave function an eigenfunction of
kinetic energy?
2 d 2
Soln. The kinetic energy operator is K . Thus,
2m dx 2
2 d 2 x2 / a 2 2 d 2 A x2 /a2
K x Ae xe
2m dx 2m dx a 2
2 2
2 d 2 A x2 / a2 2 A 2 2 x x2 / a 2 x 2 / a 2 A 2 x x2 / a 2
xe x e e 1 e
2m dx a 2 2 2
ma 2
a 2
2 ma a
This is not an eigenfunction of kinetic energy.
Example 11: An operator A is defined as A x * x x . Is this a linear operator?
Soln. For the given operator,
*
A 1 x 2 x 1 x 2 x 1 x 2 x
*1 x *2 x 1 x 2 x
*1 x 1 x *2 x 2 x *1 x 2 x *2 x 1 x
Concept of wave function 31
and A 1 x A 2 x *1 x 1 x *2 x 1 x
i 2 p2
Example 12. Prove that Xpx , H p x X p x ,V where H x V , and V is potential energy
m 2m
operator.
p2 p2
Soln. Xpx , H X px , H X , H px = X p x , x V X , x V px
2m 2m
1
X px , V
2m
px X , p x X , px px p x
1 i
X px , V 2ip x p x p x2 X px , V
2m m
Example 13. 1 and 2 be two ortonormal state vectors. Let A 1 2 2 1 . Is a projection
operator?
† † †
Soln. A† 1 2 2 1 1 2 2 1 2 1 1 2 A
Hence, A is hermitian.
2
Now, A 1 2 2 1 1 2 2 1
1 2 1 2 2 1 2 1 1 2 2 1
1 2 | 1 2 1 2 | 2 1 2 1 | 1 2 1 | 2 1
d 2 1 2 1 2 px2
Soln. x X ,H X , V x
dt i i 2m
1 2 2 1
X , px px X 2 , px X 2 , px p x
2mi 2mi
1 1 1
p x 2iX 2iX p x px X Xpx Xpx px X
2mi m m
Example 15. Prove that the operators i (d / dx) and d 2 / dx 2 are Hermitian.
*
* d * d * d
Soln. m i dx n dx i[ m n ] i n dx mdx i m n dx
dx
Therefore, id / dx is Hermitian.
d 2 n
* * dn d n d *m
dx2m dx
m dx dx
dx dx
32 Concept of wave function
d * d 2 *m d 2 *m
m n n dx dx 2 n dx
dx dx 2
Thus, d 2 / dx 2 is Hermitian.
Example 16: Find the following commutation relations:
2
(i) x , x 2 (ii) , F ( x )
x
2 2 2 3 3
Soln. (i) , 2 2
2 3 3
0
x x x x x x x x
F F
(iii) , F ( x ) ( F ) F = F F
x x x x x x x
F
Thus, , F ( x)
x x
Example 17: Find the equivalence of the following operators:
d d d d
(i) x x (ii) x x
dx dx dx dx
d d d d
Soln. (i) x x ( x) x x
dx dx dx dx
d 2 d d d2 d
= x x x 2
= 2
2 x x 2 1
dx 2 dx dx dx dx
2
d d d d
Therefore, x x 2
2x x2 1
dx dx dx dx
2
d d d 2
(ii) Similarly, x x 2 x 1
dx dx dx
Example 18. By what factors do the operators ( x 2 px2 px2 x 2 ) and 1 / 2( xpx px x) 2 differ?
2 2 f 2 (x2 f )
( x p p x ) f x
2 2 2 2 2
Soln. x 2
x x 2
x
2 f 2
2 ( x f ) 2 x 2
2 f f
x
2 2
2
2 2 xf x 2
x 2
x x x x x
2 f f 2 f f 2
2 x2 2 2 f 2 x x2 2 2 x 2 2 x2 2 4 x 2 f
x x x x x x
1 i f ( xf )
( xpx px x) 2 f ( xpx px x ) x
2 2 x x
Concept of wave function 33
i f
( xpx px x) 2 x f
2 x
2 f f f ( xf )
x 2 x x 2 x2
2 x x x dx x x
2 2 2 f f f 2
2 f f f
2x 2
2x x 2x 2
4x x f
2 x x x x x x
2 f 2
2 f 2 2
2
1
8 x 2 x 2
f 2 x 2
4x f
2 x x x x 2
Note:
(1) If the state of the particle is an eigenfunction of the operator  , then the expectation value of the physical
observable corresponding to  will be equal to the eigenvalue of  corresponding to the state of the particle.
(2) The state of the particle is given as:
C1 1 C2 2 C3 3 ................. Cn n
n
where 1 , 2 .......... are the eigenfunction of the operator  , then expectation value of the the physical
observable corresponding to  will be
2
Aˆ Cn n
n
Example 20: A particle of mass ‘m’ is confined in a 1-D box from x 2 L to x 2 L . The wave function
x
of the particle in this state is x 0 cos
4L
(i) Find the normalization factor.
(ii) The expectation value of P2 in this state.
2L 2L
* 2 2x 2 1 2 x
Soln. (i) dx 1 0 2 L cos 4 L dx 1 0 2 L 2 1 cos 4L dx
2 2 2 L
0 2 x 4 L 0 1
x sin 1 2 L 2 L 1 0
2 4 L 2 2 L 2 2L
d2 2
P 2 * 2 2 dx = cos 2 x
2
2L 2L
2 L dx dx
2 L 2 L 4 L 4 L
2 2 1 2 L x 2 2 2L x 2 2
1 cos dx 1 cos
2 L 16 L2 2 2 L
. dx =
2L 32 L3 0
2L 16L2
Example 21: Find the expected value of position and momentum of a particle whose wave function is
2 / a 2 ikx
x e x in all space
2 / a2
*
x dx e 2 x .xdx
Soln. Expected position of the particle x 2 / a2
0
*
dx e 2 x dx
Example 22. The wavefunction of a particle in a state is N exp( x 2 / 2) , where N (1/ )1/4 .
Evaluate ( x ) ( p) .
2 N 2 x2 2 N 2 2 x2
exp
dx x exp dx
2
Concept of wave function 35
2 2 2
2 2
2
x2 x p2 p
2 2
Therefore, xp
2 2 2
Example 23. The Hamiltonian operator of a system is H (d 2 / dx 2 ) x 2 . Show that Nx exp( x 2 / 2)
is an eigenfunction of H and determine the eigenvalue. Also evaluate N by normalization of the function.
Soln. Nx exp( x 2 / 2), N being a constant
d2 x2 x2 d x2 x 2
H 2 x 2 Nx exp Nx3 exp exp x 2 exp
dx 2 2 dx 2 2
x2
3 Nx exp 3
2
Thus, the eigenvalue of H is 3. The normalization condition gives
1/ 2
2 2 x2 2
N xe dx 1 N 2
2
1 N
1/ 2
2 x2
The normalized function x exp
2
x2
Example 24. Consider the wave function ( x ) A exp 2 exp(ikx) , where A is a real constant.
a
(i) Find the value of A, (ii) calculate p for this wave function.
2 2x2
Soln. (i) Normalization condition: A a 2 dx 1
exp
1/ 2
2
A2 2
1 A a
2/ a
d x 2 ikx 2 x x 2 ikx
(ii) p * i
dx dx ( i ) A 2
a 2 a2 a 2 e dx
exp e ik exp
2 2 x 2 2 x 2
(i) 2 exp 2 xdx (i)(ik ) A2 exp 2 dx
a a a
In the first term, the integrand is odd and the integral is from to . Hence the integral vanishes.
2 x 2
Therefore, p k , since A 2
a 2 dx 1
exp