Thursday, June 16, 2016

Hydrogen bonds and infrared absorption intensity

I just posted a preprint
Bijyalaxmi Athokpam, Sai G. Ramesh, Ross H. McKenzie

We consider how the infrared intensity of an O-H stretch in a hydrogen bonded complex varies as the strength of the H-bond varies from weak to strong. We obtain trends for the fundamental and overtone transitions as a function of donor-acceptor distance R, which is a common measure of H-bond strength. Our calculations use a simple two-diabatic state model that permits symmetric and asymmetric bonds, i.e. where the proton affinity of the donor and acceptor are equal and unequal, respectively. The dipole moment function uses a Mecke form for the free OH dipole moment, associated with the diabatic states. The transition dipole moment is calculated using one-dimensional vibrational eigenstates associated with the H-atom transfer coordinate on the ground state adiabatic surface of our model.

Over 20-fold intensity enhancements for the fundamental are found for strong H-bonds, where there are significant non-Condon effects

The isotope effect on the intensity yields a non-monotonic H/D intensity ratio as a function of R, and is enhanced by the secondary geometric isotope effect.

The first overtone intensity is found to vary non-monotonically with H-bond strength; strong enhancements are possible for strong H-bonds.
(see the figure below)
This is contrary to common assertions that H-bonding decreases overtone intensity.

Modifying the dipole moment through the Mecke parameters is found to have a stronger effect on the overtone than the fundamental. We compare our findings with those for specific molecular systems analysed through experiments and theory in earlier works. Our model results compare favourably for strong and medium strength symmetric H-bonds. However, for weak asymmetric bonds we find much smaller effects than in earlier work, raising questions about whether the simple model used is missing some key physical ingredient in this regime.

Comments are welcome.

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