Hydrogen bonding and vibrational energy relaxation of interfacial water: A full DFT molecular dynamics simulation

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Title
Hydrogen bonding and vibrational energy relaxation of interfacial water: A full DFT molecular dynamics simulation
Author(s)
Jonggu Jeon; Cho-Shuen Hsieh; Yuki Nagata; Mischa Bonn; Minhaeng Cho
Publication Date
2017-07
Journal
JOURNAL OF CHEMICAL PHYSICS, v.147, no.4, pp.044707 -
Publisher
AMER INST PHYSICS
Abstract
The air-water interface has been a subject of extensive theoretical and experimental studies due to its ubiquity in nature and its importance as a model system for aqueous hydrophobic interfaces. We report on the structure and vibrational energy transfer dynamics of this interfacial water system studied with equilibrium and non-equilibrium molecular dynamics simulations employing a density functional theory -based description of the system and the kinetic energy spectral density analysis. The interfacial water molecules are found to make fewer and weaker hydrogen (H)-bonds on average compared to those in the bulk. We also find that (i) the H-bonded OH groups conjugate to the free OH exhibit rather low vibrational frequencies (3000-3500 cm-1); (ii) the presence of a significant fraction (>10%) of free and randomly oriented water molecules at the interface (labile water), neither of whose OH groups are strong H-bond donors; (iii) the inertial rotation of free OH groups, especially from the labile water, contribute to the population decay of excited free OH groups with comparable rate and magnitude as intramolecular energy transfer between the OH groups. These results suggest that the labile water, which might not be easily detectable by the conventional vibrational sum frequency generation method, plays an important role in the surface water dynamics. © 2017 Author(s)
URI
https://pr.ibs.re.kr/handle/8788114/3808
ISSN
0021-9606
Appears in Collections:
Center for Molecular Spectroscopy and Dynamics(분자 분광학 및 동력학 연구단) > Journal Papers (저널논문)
Files in This Item:
Jeon-JCP-2017-DFT-MD-air-water interface_전종구.pdfDownload

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