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Title: Molecular dynamics study of two-dimensional sum frequency generation spectra at vapor/water interface

Two-dimensional heterodyne-detected vibrational sum frequency generation (2D HD-VSFG) spectra at vapor/water interface were studied by molecular dynamics (MD) simulation with a classical flexible and nonpolarizable model. The present model well describes the spectral diffusion of 2D infrared spectrum of bulk water as well as 2D HD-VSFG at the interface. The effect of isotopic dilution on the 2D HD-VSFG was elucidated by comparing the normal (H{sub 2}O) water and HOD water. We further performed decomposition analysis of 2D HD-VSFG into the hydrogen-bonding and the dangling (or free) OH vibrations, and thereby disentangled the different spectral responses and spectral diffusion in the 2D HD-VSFG. The present MD simulation demonstrated the role of anharmonic coupling between these modes on the cross peak in the 2D HD-VSFG spectrum.
Authors:
 [1] ;  [2] ;  [3]
  1. Department of Applied Chemistry, Graduate School of Science and Engineering, University of Toyama, Toyama 930-8555 (Japan)
  2. Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan and Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Kyoto 615-8520 (Japan)
  3. Molecular Spectroscopy Laboratory, RIKEN and Ultrafast Spectroscopy Research Team, RIKEN Center for Advanced Photonics (RAP), 2-1 Hirosawa, Wako 351-0198 (Japan)
Publication Date:
OSTI Identifier:
22415890
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 21; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHEMICAL BONDS; COMPARATIVE EVALUATIONS; COUPLING; DECOMPOSITION; DIFFUSION; HEAVY WATER; INFRARED SPECTRA; INTERFACES; ISOTOPE DILUTION; MOLECULAR DYNAMICS METHOD; SPECTRAL RESPONSE; TWO-DIMENSIONAL SYSTEMS; VAPORS