Supplement to Slide 22 of Preamble

1
 “Hot” band reflects
population of first
excited vibrational level
(v=1)

Notice that many

rotational levels are Fundamental absorption
populated as the resonance reflects
energy spacing is ground-state population
<<kBT (v=0) Energy gap
between v=0 and
v=1 is 667 cm-1

× × × . ×
Relative population of v=1:v=0 ~ = 0.04
. × ×

. × ×
Quick estimate: the value of kBT in cm-1 is × × . ×
= 207

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• Closely-spaced resonances on either side of the main peak at 667 cm-1 are due to molecular rotation.
(Details much later)
• The reason there are many of these resonances is that the rotational energy levels have energy values
<kBT, so that many of them have a similar probability of being populated at 298 K. (Details much later)
• The relevant equation is:
*+
! "#"$% = & ' ( ! % )! $ × ,- . ≈ (0$!($

• The reason the vibrational “hot” band (~720 cm-1) is significantly weaker than the very strong
112
fundamental absorption near 667 cm-1 is because the population in the v=1 level is only about 2 ≈

0.04 of the population in the ground state (v=0).

• In order to compare the intensities of the fundamental and the hot band, one strictly needs to convert the
transmission numbers to absorbances (Beer-Lambert Law). However, I suggest we just accept this for the
moment. (If you are curious, see Homework example 15-38. The fractional transmission would be I/I0 in
that example).