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Title: IR spectral assignments for the hydrated excess proton in liquid water

The local environmental sensitivity of infrared (IR) spectroscopy to a hydrogen-bonding structure makes it a powerful tool for investigating the structure and dynamics of excess protons in water. Although of significant interest, the line broadening that results from the ultrafast evolution of different solvated proton-water structures makes the assignment of liquid-phase IR spectra a challenging task. In this paper, we apply a normal mode analysis using density functional theory of thousands of proton-water clusters taken from reactive molecular dynamics trajectories of the latest generation multistate empirical valence bond proton model (MS-EVB 3.2). These calculations are used to obtain a vibrational density of states and IR spectral density, which are decomposed on the basis of solvated proton structure and the frequency dependent mode character. Decompositions are presented on the basis of the proton sharing parameter δ, often used to distinguish Eigen and Zundel species, the stretch and bend character of the modes, the mode delocalization, and the vibrational mode symmetry. We find there is a wide distribution of vibrational frequencies spanning 1200-3000 cm -1 for every local proton configuration, with the region 2000-2600 cm -1 being mostly governed by the distorted Eigen-like configuration. Finally, we find a continuous red shift of the special-pair O∙∙∙H +∙∙∙O stretching frequency, and an increase in the flanking water bending intensity with decreasing δ. Also, we find that the flanking water stretch mode of the Zundel-like species is strongly mixed with the flanking water bend, and the special pair proton oscillation band is strongly coupled with the bend modes of the central H 5 O 2 + moiety.
ORCiD logo [1] ; ORCiD logo [1] ;  [1] ; ORCiD logo [1] ;  [1]
  1. Univ. of Chicago, IL (United States). Dept. of Chemistry. James Franck Inst. Inst. for Biophysical Dynamics
Publication Date:
Grant/Contract Number:
SC0005418; SC0014305; ACI-1053575
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 15; Journal ID: ISSN 0021-9606
American Institute of Physics (AIP)
Research Org:
Univ. of Chicago, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; infrared spectra; hydrogen bonding; protons; normal modes; vibration analysis; electron densities of states; cluster spectra; acids; cluster analysis; absorption spectra
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1361819