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Problem Set Solutions CHAPTER 2, Levine, Quantum Chemistry, 5

The experimental value is 217 nm. The particle in a box model provides a crude estimate that is reasonably close to the experimental value.

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463 views8 pages

Problem Set Solutions CHAPTER 2, Levine, Quantum Chemistry, 5

The experimental value is 217 nm. The particle in a box model provides a crude estimate that is reasonably close to the experimental value.

Uploaded by

Marcos Vinícius
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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PROBLEM SET SOLUTIONS

CHAPTER 2, Levine, Quantum Chemistry, 5th Ed.

2.2 (A) s1 = s2 = s & y = esx is a solution of y'' + p y' + q y = 0.


Verify that y = x esx is also a solution.

If y = x esx, then y' = esx + xs esx = (1 + xs) esx &

y" = s esx + (1+xs) s esx = (2 + xs) s esx

So y'' + p y' + q y = (2 + xs) s esx + p (1 + xs) esx + q x esx

= (2s + xs2 + p + psx + qx) esx

= [xs2 + (2 + px)s + (p + qx)] esx

From the auxiliary eq.: s2 + ps + q = 0 s = -p/2 + 0.5 (p2 -


4q) = s1, s2

If s1 = s2, then p2 - 4q = 0 & p = (4q) or q = p2/4. Also s = -p/2

So [xs2 + (2 + px)s + (p + qx)] esx

= [x p2/4 + 2(-p/2) + px (-p/2) + (p + x p2/4)] e-px/2

= [x (p2/4 - p2/2 + p2/4) - p + p] e-px/2

=0
2.2 (B) Solve y" - 2 y' + y = 0.

p = -2, q = 1, y = esx s2 + p s + q = 0

s = 0.5 [-p + (p2 - 4q)] = 0.5 [ -(-2) + (4 - 4)] = 1

y = x esx = x ex, y' = ex + x ex = (1 + x)ex

y" = ex + (1 + x)ex = (2 + x)ex

Verify that y" - 2 y' + y = 0:

(2 + x)ex - 2 (1 + x) ex + x ex = 2 + x -2 -2x + x = 0
2.5 Particle with quantum number n in box of length L

(A) Determine the probability of finding the particle in the


left quarter of the box.

Region I: x < 0, V =

Region II: 0 < x < L, V = 0

Region III: x > L , V =

In the left quarter of the box: 0 < x < L/4

Probability of finding the particle in left quarter = 0 L/4II2 dx

= 0 L/4 [(2/L) sin (nx/L)] 2 dx

= (2/L) 0 L/4 [ sin (nx/L)] 2 dx

= (2/L) [x/2 - (L/4n) sin (2nx/L)]0 L/4 (See (A.2) in Table


A.5 in Appendix)

= (2/L) [L/8 - (L/4n) sin (2nL/(L4)) - 0 + 0]

= 1/4 - (1/(2n)) sin (n/2)

Probability depends on the quantum # n.


(B) For what value of n would the probability be a
maximum?

n Probability
1 1/4 - 1/(2)
2 1/4 - 1/(4) (0) = 1/4
3 1/4 - 1/(6) (-1) = 1/4 + 1/(6)
MAXIMUM
4 1/4 - 1/(8) (0) = 1/4
5 1/4 - 1/(10) (1) = 1/4 - 1/(10)
6 1/4 - 1/(12) (0) = 1/4
7 1/4 - 1/(14) (-1) = 1/4 +
1/(14)
8 1/4 - 1/(16) (0) = 1/4
Etc. Etc.

(C) As n , Probability 1/4 - (1/) (oscillating

function) = 1/4

(D) Bohr Correspondence Principal: quantum mechanics

approaches classical mechanics in the limit of large

quantum number.
2.7 Model the electron in an atom (or molecule) as a particle in a

box of diameter of the atom (or molecule).

(A) For an electron in a box of length 1 Angstrom calculate the

separation between the lowest two levels.

L = 1 Angstrom, 1 J = 1 kg m2/s2, 1 Angstrom = 10-8 cm = 10-10

m, 10-20 m2 = 1 Angstrom2

E = E2 - E1 = (22 - 12) (h2/(8mL2)

= 3 (6.63x10-34 J s)2 / [8 (9.11x10-31 kg) (1.0 Angstrom)2 (10-8

cm/1.0 Angstrom)2 (10-2 m/1 cm)2]

= 1.81x10-17 J

(B) Calculate the wavelength of a photon corresponding to a

transition between these two levels.

E = h = h c / = h c/ E = (6.63x10-34 Js) (3.00x108 m/s)/

(1.81x10-17 J)

= 10.99x10-9m
= 10.99 nm

(C) This wavelength is in the ultraviolet (uv) portion of the

electromagnetic spectrum.
2.15 A crude model of pi electrons in a conjugated molecule is

as particles in a box of length slightly longer than the conjugated

chain. The Pauli Exclusion Principle states that no more than 2

electrons (with opposite spins) can occupy one box level. For

butadiene, CH2=CHCH=CH2, take the box length as 7.0

Angstroms & use this model to estimate the wavelength of light

absorbed when a pi electron is excited from the highest occupied

to the lowest unoccupied box level. (The experimental value is

217 nm.)

There are 2 double bonds, or 4 pi electrons. If only 2 electrons

are allowed to occupy one box level, then levels n=1 & n=2 will

be occupied (with n=2 being the highest occupied level), & level

n=3 will be the lowest unoccupied level. So an electron will be

excited from level n=2 to level n=3:

E = E3 - E2 = (32 - 22) (h2/(8mL2)


= 5 (6.63x10-34 Js)2 / [8 (9.11x10-31 kg) (7.0 Angstrom)2 10-20 m2

/1 Angstrom2]

= 6.15x10-19 J

E = h = h c / = h c/ E = (6.63x10-34 Js) (3.00x108 m/s)/

(6.15x10-19 J)

= 3.23x10-7 m (109nm/1m)

= 323 nm

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