CHEMISTRY

Assignment
Home Work DPP

Quantum Chemistry (8)

1. First order perturbation correction En1 to energy level En of a simple harmonic oscillator due to
anharmonicity perturbation x3 is given by
(a) En1 =  (b) En1 =  (c) En1 =  (d) En1 = 
2. Consider a particle in a one dimensional box of length 'a' with the following potential
V(x) =  x<0
V(x) =  x > 0, V(x) = 0 ; 0  x  a/2 V(x) = V1 a/2  x  a
Starting with the standard particle in a box Hamiltonian as the zeroth order Hamiltonial and the
potential of V1 from 'a/2' to 'a' as s perturbation, the first-order energy correction to the ground state
is

(a) 0 (b) V1 (c) V12 (d) None

3. A particle is confined to move in a 1D box of length L, the left half of the box is perturbed by V1 and
CHEM ACADEMY
right half of the box is perturbed by V1/2, First order correction to the ground state energy because of
perturbation is
(a) V1/4 (b) 3V1/4 (c) 5V1/4 (d) 3V1/2
4. A particle is confined to a one dimensional potential box with the potential V = 0 0 < x < a V =
Infinite Elsewhere
If the particle is subjected to a perturbation, within the box, W = x, where is a small constant, the
first order correction to the ground state energy is
(a) 0 (b) a/4 (c) 2 (d) a
5. Consider the statements
(i) First order correction to the ground state energy is the expectation value corresponding to perturbed
part of Hamiltonian when we take perturbed part of function into consideration.
(ii) When the value of first order energy correction because of perturbation becomes zero then we
apply second order or higher order perturbation.
(iii) perturbation method generally apply when the deviaation of the real system from ideality is
large.
Correct statements above are
(a) i, ii (b) ii, iii (c) i, ii, iii (d) ii only
6. An osciallator is governed by the potential V = (k/2)x + (/6)x + (b/24) x4 using a harmonic
2 3

oscillator as an unperturbed problem, calculate the first order correction to the energy of the ground
state in simple harmonic oscillator is
(a) b/32 2 (b) b/32  (c)  b/32 2 (d) b/32 2

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7. When we operate perturbed part of Hamiltonian H1 = P sin= {1/eim}
(a) P (b) P/2 (c) P2/42 (d) 0
8. Particle is confined to move in a 1D box ofl length –L to +I, the system is perturbed by b(a–x) then
first order correction to the ground state energy is
(a) ba/2 (b) ba (c) ba/4 (d) 2ba
9. A aprticle is confined to move in 1D box of length 2a (–a < x <a) with V = 0 inside and infinite else
where
If the system is perturbed by V = {x-(a/2)} then first order energy correction to first excited state
is
(a) 0 (b) 2/a (c) 1/a (d) 1/2a
10. A particle in a 1-dimensional box of length L is perturbed by a delta function potential, (x–L/4), in
the middle of the box. The first order energy correction to the ground state will be
(a) 0 (b) 1/L (c) L/2 (d) 2/L
11. A one-dimensional box potential is perturbed so that it is raised by a constant amount, , in the left
half of the box, and lowered by  in the right half then first order correction in energy.
(a) Zero in ground state because it is symmetric but non zero in first excited state because it is
antisymmetric
(b) Non zero in ground state because it is symmetric but zero in first excited state because it is
antisymmetric
(c) Zero in both ground and first excited state

12.
CHEM ACADEMY
(d) non-zero in both ground and first excdited state
Consider the statement
(i) first-order correction tot he energy is the expectation value for the perturbation operator calculated
using the wavefunction of the perturbed system.
(ii) Particle is confined to move in 1D box of length L box is perturbed by amount x2 first order
correction to the energy is L2/3.
(iii) When perturbative correction is applied on the ground state, the second order correction to
energy is always positive
The correct statement above are
(a) i, ii (b) ii, iii (c) 1, iii (d) none
13. The normalized wavefunction of a particle in one dimensional potential well

0 if 0  x  a
Vx 
 otherwise

2  nx 
are given by  n  x   sin   , where n=1,2,3....
a  a 
The particle is subjected to a perturbation

 x  a
V '  x   V0 cos   for 0  x 
 a  2
=0 otherwise
The shift in the ground state energy due to the perturbation, in the first order perturbation theory, is

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 2V0 V0 V0 2V0
(a) (b) (c)  (d) 
3 3 3 3
14. If the perturbation H = ax where a is constant is added to the finite square well potential V = 0 for
0 < x < , V = infinite otherwise
(a) a (b) a (c) a (d) a
15. A one-dimensional quantum harmonic oscillator is perturbed by a potential x3. The first order
correction to the energy for the ground state E 10 is

(a) E 10  0 but <1 (b) E 10  0 (c) E 10 =0 (d) E 10  2

16. The following are the three statements about perturbation theory
(i) Second order perturbation correction to the ground state energy is ALWAYS negative.
(ii) Sum of the zeroth drder and the first order corrections to the ground state energy is greater than
the exact ground state energy.
(iii) Sum of the zeroth order and first order correction to the ground state energy is less than the
exact state energy. From the following which one is correct?
(a) Only (i) is true (b) Both (i) and (ii) are true
(c) Only (iii) is true (d) Both (ii) and (iii) are true
17. Consider a one-dimensional infinite square well
V = 0 for 0 < x < a

CHEM ACADEMY
V = infinite otherwise
If a perturbation V = V0 for 0 < x < a/3, and V = 0 otherwise, is applied, then the correction to the
energy of the first excited state, to first order in V, is nearest equal to
(a) V0 (b) 0.16 V0 (c) 0.2 V0 (d) 0.33 V0
18. A one dimensional simple harmonic oscillator with Hamiltonian H 0   p 2 /2m    0.5 kx 2  is
subjected to a small perturbation H1 = x +  x3 + x4The order correction to the ground state
energy is dependent on
(a) Only  (b)  and  (c)  and  (d) Only 
19. The following are the three statements about perturbation theory
(i) Second order perturbation correction to the ground state energy is ALWAYS negative.
(ii) The energy correction because of first order perturbation is generally positive.
(a) Only A is true (b) Both B is true (c) Both A and B is true (d) None
20. The ground state of a certian system with energy 0 is subjected to a perturbation V, yielding a first
order correction 1. If is the true ground-state of the perturbed system E0, the inequality that always
holds is

(a) 1  0 (b) 0  E 0 (c) 0  1  E 0 (d)  0  1  E 0

21. For a particle in a square box of length 1 with origin at x = 0 and y = 0, if the system is perturbed by
H = b for 1/4 <x<31/4, 1/4<x<31/4 Where b is constant and H = 0 elsewhere Find E11.
If the perturbation H = ax where a is constant is added to the finite square well potential V = 0 for
0<x<, V = infinite otherwise.
(a) a/2 (b) a (c) a/4 (d) a/(2)0.5

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22. The quantum state of a particle moving in a circular path in a plane is given by = (2)–1/2 eim for
rotating particle in m state) when a perturbation H1 = Pcos is applied (P is constant), what will be
the first order correction to the energy of the mn state is
(a) 0 (b) P/2 (c) P/4 (d) Pm2/42
23. A particle is confined to move in 1 D box of length L, if system is perturbed by x-(L/2) Then
first order energy correction to the ground state is
(a) 2/L (b) L/2 (c) 1/L (d) 0
24. A hydrogen atom is in an electric field of strength C. The Hamiltonian operator for this system is as
given H = H     / 2 m e   2   e 2 /4  o r   eCr cos  . The first order correction to ground state energy
of hydrogen atom is
(a)   (b)  /2 (c)  (d) 0
NET Previous Year
1. The unperturbed energy levels of a system are 0  0,1  2 and 2  4 . The second order correction
to energy for the ground state in pressure of the perturbation V for which V10 = 2, V20 = 4 and V12
= 6 has been found to be [NET June 2011]
(a) 6 (b) 0 (c) +6 (d) –8

2. For non-degenerate perturbation theory for ground state, with E (0)

0
as zeroth order energy, E (1)
0
as
the first order perturbation correction and E0 as the exact energy, which of the following is true?

(a) (E (0) (1)

0  E0 )
CHEM ACADEMY
is always equal to E0 (b) (E (0) (1)
0  E0 )  E0
[NET Dec. 2011]

(c) (E (0) (1)

0  E0 )  E0
(d) E (0) (1)
0  (E 0  E 0 )

3. Consider a particle in a one dimensional box of length ‘a’ with the following potential
[NET Dec. 2013]
V x   x0
V x   x0
V x  0 x  0x a / 2
V  x   V1 1/ 2  x a
Starting with the standard particle in a box hamiltonian as the zeroth order Hamiltonian and the
potential of V1 from ‘a/2’ to ‘a’ as a perturbation, the first – order energy correction to the ground
state is
(a) V1 (b) V1/4 (c) –1V1 (d) V1/2
4. A particle in a one dimensional harmonic oscilator in x – direction is perturbed by a potential x(
is a number). The first – order correction to the energy of the ground state.
[NET June 2014]
(a) is zero (b) is negative
(c) is positive (d) may be negative or positive but NOT zero

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5. Which of the following statements on ground state perturbation theory, involving the zeroth order
energy E00  , first order energy correction E01 and second order energy correction E 02  , is false?
[NET June 2018]
(a) E01 is the average value of perturbation operator with respect to the ground state of the zeroth
order Hamiltonian.

(b) E 01 is necessarily negative. (c) E02  is necessarily negative.

(d) E 00   E 01 is an upper bound to the exact ground state energy..
6. A particle in a 1 – dimensional box of length L is perturbed by a delta function potential, (x-L/2),
in the middle of the box. The first order energy correction to the ground state will be
 Hint :  f  x    x  a  dx  f  a  
  
. [NET Dec. 2014]
(a) 0 (b) 1 (c) L/2 (d) 2/L
7. The ground state of a certain system with energy 0 is subjected to a perturbation V, yielding a first-
order correction 1. If E0 is the true ground – state energy of the perturbed system, the inequality
that always holds is [NET Dec. 2016]
(a) 1  0 (b) 1  E0 (c) 0  1  E0 (d) 0  1  E0
8. A one – dimensional quantum harmonic oscillator is perturbed by a potential x3. The first order
correction to the energy for the ground state (E(1)) is [NET Dec. 2017]
CHEM ACADEMY
(a) E  i   0 but  1 (b) E 1  0 (c) E 1  0 (d) E 1  2
9. For a one-dimensional (x) harmonic oscillator perturbed by an x3 potential, the sum of the first
order and second order corrections to the ground state energy is [NET Dec. 2018]
(a) < 0 (b) 0 (c) > 0 (d) > 0
GATE Previous Year
1. A one – dimensional anharmonic oscillator is treated by perturbation theory. The harmonic oscilla-
1 3
tor is used as the unperturbed system and the perturbation is  x ( is a constant). Using only the
6
first order correction, the total ground state energy of the anharmonic oscillator is
[GATE 2018]
1/4 1.2
   x 2  k 
(Note: For a one – dimensional harmonic oscillator  0  x     e ;   2  )
 h 
1/2 1/2 1/2 1/2
1 k 1  k 1  k 1   k
(a)    (b)       (c)       (d)      
2  2 6   2 3   2 12    
2. The quantum state of a particle moving in a circular path in a plane is given by

 
 m     1/ 2 eim , m  0, 1, 2,.....
When a perturbation H1 = P cos  is applied (P is a constant), what will be the first order correction
to the energy of the mth state [GATE 2007]

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 (a) 0 (b) P /  2  (c) P /  4  
(d) Pm 2 / 4 2 
3. First order peturbation correction  n 1 to energy level n of a simple harmonic oscillator due to
the anharmonicity perturbation x 3 is given by [GATE 2005]

(a)  n 1   (b)  n 1   2 (c)  n 1   1 (d)  n 1  0

4. A perturbation V =  (x–a/2) is introduced in the box. The first order energy correction to the
first excited state is. [GATE 2006]
(a) 0 (b) 2/a (c) 1/a (d) 1/2a
5. A particle in one dimensional box of length 2a with potential energy

 0 x a
V
 x a

is perturbed by the potential V´ = ex eV, where c is a constant. The first order correction to the first
excited state of the system is _________ × c eV.
TIFR Previous Year
1. As electron is confined to a 2-D square potential well with dimension of 10 nm and well depth of
1eV. For a bound state, what is the maximum possible value of nx? [TIFR 2019]
(a) 0
CHEM ACADEMY
(b) Can not be determined from the information provided
(c) 266
(d) 16
Ans. d
ANSWER KEY
Assignment (8)
1. d 2. c 3. b 4. c 5. d 6. d 7. d
8. b 9. c 10. b 11. c 12. c 13. a 14. a
15. c 16. b 17. d 18. d 19. c 20. d 21. a
22. a 23. a 24. d
NET Previous Year
1. a 2. c 3. d 4. a 5. b 6. d 7. c
8. c. 9. a
GATE Previous Year
1. a 2. a 3. d 4. c 5. 0 to 0
TIFR Previous Year
1. d
HINT & SOLUTION
NET Previous Year
1. Second order perturbation for nth state is given by

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  0 | H ' | 0 
m n 
E (2)
n   
m n E 0n  E m
0

(V10 )2 (V20 )2
22 42
 0    = – 2 + (–4) = – 6
E0  E10 E 00  E02 0  2 0  4
Correct answer is (a)
2. According to “The variation principle” If any orbitary wavefunction is used to calculate the energy,
the value calculated is never less the true energy.
 Energy calculated by using an arbitary wavefunction and applying perturbation will always be
greater than or equal to true energy.

 (E (0) (1)
0  E0 )  E0

Correct answer is (c)

3. Particle in a box hamiltonian as zeroth order hamiltonian and potgential vi from a/2 to a.
a a
2 nx 2 nx 2 2 nx
 sin V1 sin dx   a V sin 1 dx
a/2
a a 1 a a/2 a

a cos 2nx
2 nx 1
 V1  sin2 dx nx a
 sin 2 
a a/2
CHEM ACADEMY
a
a 2

cos2nx
2
a 1 dx 2 1 a a
cos 2nx 
 V1  a  V1    ldx   dx 
a a/2 2 a 2  a /2 a /2
a 
a
2 1 a a  2nx  
  V1   x a / 2  sin 
a 2  2n  a  a /2 

2 1  a  a 
  V1    a    sin 2n  sin n
a 2   2  2n 
Since, sin n = 0, sin 2n = 0

2 1a a
  V1     0  0 
a 2  2 2nm 

2 1 a  V
  V1     1
a 2  2 2

n 2 h 2 V1
 E  (Perturb part)
8a 2 2
Correct answer is (d)

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 1/ 4 1/ 4
   x 2 / 2
  2

4.     e x   ex / 2 dx

1/2 1/ 2
 
 x 2  
 x 2
 

 x e dx       x e dx
n is odd. So, total integration is zero.
 2

 x n e x dx  0 if n is odd


 2

 x n e x dx  0 if n is even.


Correct answer is (a)

5. (b) First corrected energy is Ground state
E10   0 | H ' | 0

   0 H '  0 dx

= (+) ve value, (Never be negative)

Note: Only second corrected energy in ground state is always negative
2
2 m H' 0 
E 

Where m > n,
0

CHEM ACADEMY
E0  Em '

Second corrected energy in G.S.

2
2 m H' 0 
E 0
E0  Em
Em  E0
 E02  ()Ve
L
2 nx  L 2 nx
6.  sin  x   sin dx
0
L L  2 7 L

 L L
Dirac – delta condition,   x    0, x 
 2 2
L
The value of x 
2
Between the 0  L
L
So, direct put the value of x  in the wavefunction and n = 1, no integration.
2
L L 2 L
sin sin
2 L 2 L L 2
2   2   
sin sin   sin  1
L 2 2 7  2 

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 Correct answer is (d)
7. According to Perturbation theory, “The energy of perturbed system is equal or greater than the
standard system.”
Correct option is (c)
8. For odd power of perturbed potential, E(1) is always ‘0’
Correct option is (c)
9. For 1-D harmonic oscillator, wavefunction of the particle in the ground state, will have even parity
(defined parity). Therefore, first order correction to ground state energy due to a perturbing poten-
tial x3 (odd function) will be equal to zero.
For any potential system, the second ordr correction to ground state energy due to perturbation is
always negative.
So, sum of the corrections will be < 0
Correct option is (a)
GATE Previous Year
3. (d) First order correction to the ground state energy is

  1 x3e axe dx
E'0    H '  x 3 
  6
Since, H’ is odd i.e., x3, the E’ will be zero.

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