Department of Physics and Chemistry, IIT Tirupati
PH105L: Introduction to Quantum Science and Technology
Tutorial 9: Molecular Spectroscopy
1. Assume a quantum harmonic oscillator with zero-point energy 1084.9 cm−1 and using
this calculate and comment on the population of CO molecules at upper vibrational
state (ν = 1) at room temperature (25.0◦ C) with respect to the ground state. Given
kB = 0.69503476 cm−1 K−1 .
2. Consider a molecule with donor–acceptor fragments separated by a distance R. The
charge transfer energy hνCT is given by
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hνCT = IP (D) − EA(A) −
εR
where IP and EA refer to the ionization potential of the donor and the electron
affinity of the acceptor, respectively. And, ε is the dielectric constant of the medium.
1. Plot hνCT as a function of R and also as a function of the inverse distance 1/R.
2. Calculate the CT energy hνCT in eV required for exciting an electron from
the Zinc-porphyrin donor to the PCBM, a C60 derivative acceptor in a toluene
medium (ε = 2.4 ).
Given: IP (Donor) = 7.0 eV, EA(Acceptor) = 2.6 eV, R = 5.29 Å
3. Using the calculated hνCT , determine the wavelength of light required for ac-
cessing this charge-transfer state, and specify the spectral region in which this
wavelength falls (e.g., UV, visible, IR).
3. What are the allowed electronic transitions that are possible for the given molecules
a) Formaldehyde b) 1,3-butadiene and also comment on the energy transition order.
4. Classify the following molecules whether rotational active or IR active? a) H2 b) F2
c) CO d) CO2 e) HCl, f) HCN. Calculate the number of vibrational modes possible
for the above IR active molecules.
5. Rotational absorption lines from H35 Cl were found at the following wavenumbers
cm−1 : 83.32, 104.13, 124.73, 145.37, 165.89, 186.23, 206.60, and 226.86. Find the
rotational constant.
6. The pure rotational spectrum of gaseous molecule HCl consists of a series of equally
spaced lines seperated by 20.80 cm−1 . Calculate the internuclear distance of the
molecule.
(Hint:The atomic masses of H =1.673 × 10−27 kg, Cl =58.06 × 10−27 kg ).
7. The fundamental vibrational frequency of HCl is 2890 cm−1 . Calculate the force
constant of this molecule. Comment on the fundamental vibrational frequency of the
isotope DCl (Hint: The atomic masses of H =1.673 × 10−27 kg, Cl =58.06 × 10−27
kg and D =3.3433 × 10−27 kg. )
8. Find the fundamental IR frequency of the C C , C C and C C. The
force constant of the C C,C C and C C are 5, 10, 15 in 10 dyne cm−1 .
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