(McQuarrie 6-44) In this problem, we'll calculate the fraction of diatomic molecules in a particular rotational level at a temperature T using the rigid rotor approximation. This fraction is governed by the Boltzmann distribution, which says that the number of molecules with energy EJ is proportional to e-EJ/kBT, where kB is the Boltzmann constant and T is the temperature in Kelvin. Because the J-th rotational level has degeneracy (2J + 1), we write, where we have used EJ = NJ = c(2J+1)e¯ −BJ(J+1)/kBT BJ(J+1). Plot NJ/No versus J for H35 C1 (B = 10.60 cm-1) and 127135 Cl (B = 0.114 cm-1) at 300 K. At approximately what rotational state J is the population ratio NJ/No a maximum in each case? Explain how this distribution of rotational state populations leads to the spectroscopic band structure of the sort seen in McQuarrie Figure 6.4 or in lecture. P branch. R branch 2400 2500 2600 2700 v/cm¹

Physical Chemistry
2nd Edition
ISBN:9781133958437
Author:Ball, David W. (david Warren), BAER, Tomas
Publisher:Ball, David W. (david Warren), BAER, Tomas
Chapter14: Rotational And Vibrational Spectroscopy
Section: Chapter Questions
Problem 14.24E: Which of the following molecules should have pure rotational spectra? a Dimethyltriacetylene,...
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(McQuarrie 6-44) In this problem, we'll calculate the fraction of diatomic molecules in a
particular rotational level at a temperature T using the rigid rotor approximation. This
fraction is governed by the Boltzmann distribution, which says that the number of molecules
with energy EJ is proportional to e-EJ/kBT, where kB is the Boltzmann constant and T is
the temperature in Kelvin. Because the J-th rotational level has degeneracy (2J + 1), we
write,
where we have used EJ
=
NJ = c(2J+1)e¯ −BJ(J+1)/kBT
BJ(J+1). Plot NJ/No versus J for H35 C1 (B = 10.60 cm-1) and
127135 Cl (B = 0.114 cm-1) at 300 K.
At approximately what rotational state J is the population ratio NJ/No a maximum in each
case? Explain how this distribution of rotational state populations leads to the spectroscopic
band structure of the sort seen in McQuarrie Figure 6.4 or in lecture.
Transcribed Image Text:(McQuarrie 6-44) In this problem, we'll calculate the fraction of diatomic molecules in a particular rotational level at a temperature T using the rigid rotor approximation. This fraction is governed by the Boltzmann distribution, which says that the number of molecules with energy EJ is proportional to e-EJ/kBT, where kB is the Boltzmann constant and T is the temperature in Kelvin. Because the J-th rotational level has degeneracy (2J + 1), we write, where we have used EJ = NJ = c(2J+1)e¯ −BJ(J+1)/kBT BJ(J+1). Plot NJ/No versus J for H35 C1 (B = 10.60 cm-1) and 127135 Cl (B = 0.114 cm-1) at 300 K. At approximately what rotational state J is the population ratio NJ/No a maximum in each case? Explain how this distribution of rotational state populations leads to the spectroscopic band structure of the sort seen in McQuarrie Figure 6.4 or in lecture.
P branch.
R branch
2400
2500
2600
2700
v/cm¹
Transcribed Image Text:P branch. R branch 2400 2500 2600 2700 v/cm¹
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