期刊
JOURNAL OF CHEMICAL PHYSICS
卷 121, 期 21, 页码 10577-10598出版社
AMER INST PHYSICS
DOI: 10.1063/1.1807824
关键词
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资金
- NIGMS NIH HHS [R01 GM 59230-04] Funding Source: Medline
The line shapes detected in coherent femtosecond vibrational spectroscopies contain direct signatures of peptide conformational fluctuations through their effect on vibrational frequencies and intermode couplings. These effects are simulated in trialanine using a Green's function solution of a stochastic Liouville equation constructed for four collective bath coordinates (two Ramachandran angles affecting the mode couplings and two diagonal energies). We find that fluctuations of the Ramachandran angles which hardly affect the linear absorption can be effectively probed by two-dimensional spectra. The signal generated at k(1)+k(2)-k(3) is particularly sensitive to such fluctuations. (C) 2004 American Institute of Physics.
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