Assigned problems for Chapter 10 on the particle in a box

1. calculate the energy separation in J, kJ mol-1 , eV, and cm-1

,
between the levels (a) n = 2 and n = 1 , ( b ) n= 6 and n = 5
of an electron in a 1- D box of length 1,0 nm

n 2h
E=
8m e L2

n 2h (6.626x10 −34 Js) 2

E= 2
= −31 −9 2
= 6.02x10 −20 j
8m e L (8)x(9.109x10 Kg)x(1.0x10 m)

The conversion factors required are

Na
E/(kJ mol -1 ) = E/ J
10

1 eV = 1.602x10 -19 J; 1 cm-1 = 1.986x10 -23 J

h −23
(a) E 2 − E1 = (4 - 1 ) 2 = 3x(6.02x10 J
8m e L

= 18.06x10 -20 J = 1.81x10 -19 J; 110kJ mol -1 ; 1.1 eV; 9100 cm-1
2. Calculate the probability that a particle
will be found between 0.49 L and 0.51L in a 1 - D
box of length L
when it has (a) n = 1 , (b) n=2.
The the wavefunction to be a constant in this range

the wavefunctions are

2  n x
= sin 
n
L  L 

The propability is

0.51L
P= ∫ n
2
dx ≈ n
2
x
0.49L

(a)

2  n x
P= sin 2   x
L  L 

For x =.5L n= 1

2  
P= sin 2   x0.02L = 0.04
L  2
3.
(a) Write the Schrödinger equation for a particle in a 1-D square well
of length L

(b) Calculate the expectation value of p and p 2 for a particle in the state n=1

Answ:

(a)
h2 d 2
− =E
2m dx 2

which has the solution

2  n x
= sin 
L  L 
n

h d
ˆp = −
i dx
L 2h L  n x  d  n x
< pˆ >= ∫ * pˆ n dx = 2 ∫ sin  sin  dx
iL 0  L  dx  L 
n
0

2h L  n x   n x
= 2 ∫ sin  cos  dx = 0
iL 0  L   L 
4. What are the most likely locations of a particle in a
box of length L in the state n = 3 ?

2  3 x
= sin  
3
L  L 

 3 x
P ( x )∝ ∝ sin 2  
3 3  L 

dP(x)
The maxima and minima in P(x) corresponds to =0
dx

dP(x)  3 x  3 x  6 x
∝ sin   cos  ∝ sin  
dx  L   L   L 

 6 x
sin = 0 when =  = n' , n = 0,1,2.....
 L 

n' L
which corresponds to x = , n'< 6.
6

n' = 0,2,4, and 6 corresponds to minima in

n' = 1, 3, and 5 to maxima

 5. Set up the Schrödinger equation for a particle of mass m in a three-
dimensional square well with

sides L x ; Ly ; Lz . Show that the wavefunction is defined by three quantum numbers

and that the Schrödinger equantion is separable . Find the energy levels, and specialize
the results to a cubic box of side L

Please see handout on particle in 3-D box (Lecture-10)

6. To a crude first approximation, a electron in a linear polyene

my be considered to be a particle in a one dimensional box.
The polyene - carotene contains 22 conjugated C atoms, and the
average internuclear distance is 140 pm. Each state up to n =11 is
occupied by two electrons.
Calculate
(a) the separation in energy between the ground state and
the first excited state in which one electron occupies the state with n=12.
(b) The frequency of the radiation required to produce a transition between
these two states
(c) The total probability of finding an electron between C atoms 11 and 12 in the
groundsate of the 22-electron molecule

Answ:

( a ) : L =(21)x(1.40x10-10 m) = 2.94x10 −9 m

h2 h2
E = E12 − E11 = (2n + 1)x = (2x11 + 1)x
8mL2 8mL2

(23)x(6.626x10 −34 Js) −19

= = 1.603x10 J = 1.60x10 −19 J
(8)x(9.11x10 −31 Kg)x(2.94x10 −9 ) 2
 E 1.603x10 −19 J
(b) : = = −34 = 2.42x10 14 s −1 = 2.42x10 14 Hz
h 6.626x10 Js

7. Consider a particle in a cubic box. What is the degeneracy of the levels

that has an energy three times that of the lowest level.