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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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Chemical exchange 2D IR of hydrogen-bond making and breaking

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Title
Chemical exchange 2D IR of hydrogen-bond making and breaking
Author
Kim, Yung SamHochstrasser, RM
Issue Date
2005-08
Publisher
NATL ACAD SCIENCES
Citation
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OFAMERICA, v.102, no.32, pp.11185 - 11190
Abstract
The involvement of chemical exchange in 2D IR heterodyne echo spectroscopy is characterized through the hydrogen-bond exchange between CH3OH and the CN of CH3CN. The exchange dynamics on the hydrogen-bond potential surfaces associated with different quantum states of the high-frequency CN stretching mode contributes to strong cross peaks between CN groups in two different chemical configurations and provides firm evidence of the hydrogen exchange between them. In analogy with NMR, the chemical exchange is seen in both slow and dynamic regimes. The relative magnitudes of the cross peaks at various population periods measure the picosecond regime time constants for H-bond transfer, whereas the temperature dependences indicate that the activation energy for the exchange from the H-bonded state to the free state is ≈6.2 kJ·mol-1. The results suggest that the hydrogen-bond dynamics is very similar in both vibrational quantum states of CN, suggesting that this stretching mode is not strongly coupled to the H-bond breaking reaction coordinate. The likely manifestations of chemical exchange in 2D IR experiments are discussed.
URI
https://scholarworks.unist.ac.kr/handle/201301/8961
URL
http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=23844509509
DOI
10.1073/pnas.0504865102
ISSN
0027-8424
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CHM_Journal Papers
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