Effect of hydrogen bonding on the infrared absorption intensity of OH stretch vibrations

Athokpam, Bijyalaxmi, Ramesh, Sai G. and McKenzie, Ross H. (2017) Effect of hydrogen bonding on the infrared absorption intensity of OH stretch vibrations. Chemical Physics, 488-489 43-54. doi:10.1016/j.chemphys.2017.03.006


Author Athokpam, Bijyalaxmi
Ramesh, Sai G.
McKenzie, Ross H.
Title Effect of hydrogen bonding on the infrared absorption intensity of OH stretch vibrations
Journal name Chemical Physics   Check publisher's open access policy
ISSN 0301-0104
1873-4421
Publication date 2017-05-11
Sub-type Article (original research)
DOI 10.1016/j.chemphys.2017.03.006
Open Access Status Not yet assessed
Volume 488-489
Start page 43
End page 54
Total pages 12
Place of publication Amsterdam, Netherlands
Publisher Elsevier BV
Collection year 2018
Language eng
Abstract We consider how the infrared intensity of a hydrogen-bonded OH stretch varies from weak to strong H-bonds using a theoretical model. We obtain trends for the fundamental and overtone transition intensities as a function of the donor–acceptor distance, a common measure of H-bond strength. Building upon our earlier work using a two-diabatic state model, we introduce a Mecke function-based dipole moment for the H-bond and calculate transition moments using one-dimensional vibrational eigenstates along the H-atom transfer coordinate. The fundamental intensity is found to be over 20-fold enhanced for strong H-bonds, where non-Condon effects are significant. We analyse isotope effects, including the secondary geometric isotope effect. The first overtone intensity varies non-monotonically with H-bond strength; suppression occurs for weak bonds but strong enhancements are possible for strong H-bonds. We also study how these trends are affected by Mecke parameter variations. For a few specific dimers, we compare our results with earlier works.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Mathematics and Physics
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