Molecular modeling and assignment of IR spectra of the hydrated excess proton in isotopically dilute water

Biswas, Rajib; Carpenter, William; Voth, Gregory A.; Tokmakoff, Andrei

doi:10.1063/1.4964723

Title: Molecular modeling and assignment of IR spectra of the hydrated excess proton in isotopically dilute water

Journal Article · Wed Oct 19 00:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4964723· OSTI ID:1465106

Biswas, Rajib ^[1];

^[1]; Voth, Gregory A. ^[1]; Tokmakoff, Andrei ^[1]

Univ. of Chicago, IL (United States). Dept. of Chemistry, James Franck Inst., and Inst. for Biophysical Dynamics

Infrared (IR) spectroscopy of the water O–H stretch has been widely used to probe both the local hydrogen-bonding structure and dynamics of aqueous systems. Although of significant interest, the IR spectroscopy of excess protons in water remains difficult to assign as a result of extensive and strong intermolecular interactions in hydrated proton complexes. As an alternate approach, we develop a mixed quantum-classical model for the vibrational spectroscopy of the excess proton in isotopically dilute water that draws on frozen proton-water clusters taken from reactive molecular dynamics trajectories of the latest generation multi-state empirical valence bond proton model (MS-EVB 3.2). A semi-empirical single oscillator spectroscopic map for the instantaneous transition frequency and transition dipole moment is constructed using potential energy surfaces for the O–H stretch coordinate of the excess proton using electronic structure calculations. Calculated spectra are compared with experimental spectra of dilute H+ in D2O obtained from double-difference FTIR to demonstrate the validity of the map. The model is also used to decompose IR spectra into contributions from different aqueous proton configurations. We find that the O–H transition frequency continuously decreases as the oxygen-oxygen length for a special pair proton decreases, shifting from Eigen- to Zundel-like configurations. The same shift is accompanied by a shift of the flanking water stretches of the Zundel complex to higher frequency than the hydronium O–H vibrations.

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Research Organization:: Univ. of Chicago, IL (United States). Dept. Chemistry, James Franck Institute, and Institute for Biophysical Dynamics

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)

Grant/Contract Number:: SC0005418; ACI-1053575; SC0014305

OSTI ID:: 1465106

Alternate ID(s):: OSTI ID: 1329330; OSTI ID: 1582240

Journal Information:: Journal of Chemical Physics, Vol. 145, Issue 15; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 17 works

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