Spectroscopy

Code: 102531

Solutions to Exercises of Unit:

I. INTRODUCTION TO SPECTROSCOPY

Exercise 1:
a) 1.048 10 Hz, ̅ 0.3493 cm .
b) 7.524 10 Hz, ̅ 2507 cm .
c) 1.048 10 Hz, ̅ 34930 cm .

Exercise 2:
a) 1075 nm.

Exercise 3:
a) It is the 5 to 7 transition.

Exercise 4:
a) For 10 s Δν 79.5 Hz
b) For 10 s Δν 795 MHz

Exercise 5:
a) For the non-degenerate excited state:
i) 29 K: 4.5 10 .
ii) 290 K: 0.269.
iii) 2900 K: 0.475. The population of the non-degenerate excited state
will never be equal to that of the ground state (as temperature increases, the
population of the excited state will resemble more and more that of the ground
state, without ever becoming the same).
b) For the 3-fold degenerate excited state: in this case we give the population of the
excited level (the population of each of the excited states will be 1/3 this value, and
are also given):
i) 29 K: 1.4 10 .
ii) 290 K: 0.525
iii) 2900 K: 0.731.The population of the excited level will equal that
of the ground state at 264 K.

Exercise 6:
a) 1.279 Å.

Exercise 7:
a) X=36.99 amu. The isotope is 37Cl.
Exercise 8:
a) HF: 100 1, 300 2, 1000 4.
b) HCl: 100 1, 300 4, 1000 5.
c) CO: 100 4, 300 7, 1000 13.

Exercise 9:
a) (Requires least-squares fitting)1
=10.396 cm-1, =0.0005 cm-1 ( 0.9995).

Exercise 10:
a) These are the first three lines of both isotopologues:
← CO 3.86 cm-1, ← CO 7.72 cm-1, ← CO 11.58 cm-1
← CO 3.68 cm-1, ← CO 7.36 cm-1, ← CO 11.04 cm-1
In a spectrum from a sample containing both isotopologues, their respective lines
would show up as distinct if the resolution of the apparatus is at least the difference
between the closest two lines (or better). This means it must separate lines 0.18 cm-1
apart.
b) Identify the J value of the line of the spectrum that has the largest intensity, and use
the equation relating the J line of maximum intensity to temperature (you ought to
have used this expression to solve problem 3 in this Unit).

Exercise 11:
a) =1.695 cm-1.
b) Δ ̅ 3.390 cm-1.
c) ← 813 GHz.
d) In a isotopically pure sample the lines of the spectrum lack satellite lines of lower
intensity.

Exercise 12:
a) =1.517 cm-1, R=1.262 Å.
b) If the Rigid Rotor model is applicable, spacing between lines should remain constant
throughout the spectrum.

Exercise 13:
a) Missing transitions are ← 2.33 cm-1 and ← 11.65 cm-1.
b) Rigid rotor is applicable (See exercise 12, question c).
c) =1.165 cm-1.
d) Boron. The experimental rotational spectrum of B2 has no lines, though.

1
“Requereix ajust per mínims quadrats.”