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Kim, Yung Sam
Ultrafast 2D IR Spectroscopy Lab
Research Interests
  • 2D IR, chemical exchange of H-bond, fast reaction dynamics, protein dynamics

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Vibrational dynamics of N-H, C-D, and C = O modes in formamide

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Title
Vibrational dynamics of N-H, C-D, and C = O modes in formamide
Author
Ha, JHKim, Yung SamHochstrasser, RM
Keywords
Correlation decays; Correlation functions
Issue Date
2006-02
Publisher
AMER INST PHYSICS
Citation
JOURNAL OF CHEMICAL PHYSICS, v.124, no.6, pp.1 - 10
Abstract
By means of heterodyned two-dimensional IR photon echo experiments on liquid formamide and isotopomers the vibrational frequency dynamics of the N-H stretch mode, the C-D mode, and the C = O mode were obtained. In each case the vibrational frequency correlation function is fitted to three exponentials representing ultrafast (few femtoseconds), intermediate (hundreds of femtoseconds), and slow (many picoseconds) correlation times. In the case of N-H there is a significant underdamped contribution to the correlation decay that was not seen in previous experiments and is attributed to hydrogen-bond librational modes. This underdamped motion is not seen in the C-D or C = O correlation functions. The motions probed by the C-D bond are generally faster than those seen by N-H and C = O, indicating that the environment of C-D interchanges more rapidly, consistent with a weaker C-D center dot center dot center dot O = C bond. The correlation decays of N-H and C = O are similar, consistent with both being involved in strong H bonding.
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DOI
10.1063/1.2162165
ISSN
0021-9606
Appears in Collections:
PHY_Journal Papers
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