Journal article
Two-dimensional infrared study of the C D and C O stretching vibrations in strongly hydrogen-bonded complexes
Chemical physics, Vol.512, pp.3-12
08/2018
DOI: 10.1016/j.chemphys.2018.05.025
Abstract
We report a study of the Csingle bondD and Cdouble bondO stretching modes of formyl deuterated formic acid (DCOOH) hydrogen bonded to nitrogenous bases. These modes are spectators to the hydrogen bond itself but are sensitive to the strength of that interaction. Using 2D IR spectroscopy, we show that in strongly hydrogen bonded complexes the Csingle bondD stretching vibration becomes anharmonically coupled to low-order combination states leading to strong state mixing resulting in Fermi resonance transitions in the 2D IR spectra. In contrast, the Cdouble bondO vibrations show multiple peaks as a result of conformational heterogeneity associated with internal rotation about the hydrogen bond. For both modes, the population relaxation rates tend to be quite short, ∼1 ps or less. Having characterized the vibrational spectroscopy of these spectator vibrations, we conclude that they are quite sensitive to details of the hydrogen bonding interactions though their utility is limited by spectral complexity and short population lifetimes.
Details
- Title: Subtitle
- Two-dimensional infrared study of the C D and C O stretching vibrations in strongly hydrogen-bonded complexes
- Creators
- Andrea B GraftonChristopher M Cheatum
- Resource Type
- Journal article
- Publication Details
- Chemical physics, Vol.512, pp.3-12
- DOI
- 10.1016/j.chemphys.2018.05.025
- ISSN
- 0301-0104
- Grant note
- DOI: 10.13039/100000001, name: National Science Foundation, award: CHE-1361765
- Language
- English
- Date published
- 08/2018
- Academic Unit
- Chemistry; Core Research Facilities
- Record Identifier
- 9983985991902771
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