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Title: Tunneling of hydrogen between molecules in solution

Abstract

This paper reports a treatment of the tunneling of hydrogen between two molecular centers in a system dissolved in a simple liquid. The purpose is to see whether spectroscopic signatures of the tunneling persist in the form of splittings of the vibrational modes. The analysis uses realistic potential energy functions for the interaction between hydrogen and its molecular skeleton. The effect of the liquid is modeled with Lennard-Jones potentials and is handled in the Born-Oppenheimer limit with the Metropolis/Monte Carlo algorithm. The calculations simulate the effect of solvent pair potentials and temperature on the splittings due to light atom tunneling. The analysis is general and should be useful for fairly complicated molecular systems. For the simple generic system considered, A-H + B {leftrightarrow} A + H-B in an argon-like solvent, observable inhomogeneous broadening can arise due to the environment. Values for the parameters in the A-H Morse potential were chosen to yield values for the splittings in the ground and excited states that were near to those found for the ammonial inversion. In liquid argon, the transitions and the associated splittings were shifted were shifted considerably when compared to the vacuum values. Moreover, there was considerable broadening. The splitting did,more » however, persist; thus, for the system examined, a spectroscopic signature of the tunneling persists and should be observable.« less

Authors:
 [1]
  1. Office of Naval Research, Arlington, VA (USA)
Publication Date:
OSTI Identifier:
6952012
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry; (USA)
Additional Journal Information:
Journal Volume: 93:18; Journal Issue: 18; Journal ID: ISSN 0022-3654
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 08 HYDROGEN; 74 ATOMIC AND MOLECULAR PHYSICS; HYDROGEN; TUNNELING; CALCULATION METHODS; LIQUIDS; MATHEMATICAL MODELS; MOLECULAR MODELS; MONTE CARLO METHOD; ELEMENTS; FLUIDS; NONMETALS; 400000* - Chemistry; 080800 - Hydrogen- Properties & Composition; 640302 - Atomic, Molecular & Chemical Physics- Atomic & Molecular Properties & Theory

Citation Formats

Schmidt, P P. Tunneling of hydrogen between molecules in solution. United States: N. p., 1989. Web. doi:10.1021/j100355a008.
Schmidt, P P. Tunneling of hydrogen between molecules in solution. United States. https://doi.org/10.1021/j100355a008
Schmidt, P P. 1989. "Tunneling of hydrogen between molecules in solution". United States. https://doi.org/10.1021/j100355a008.
@article{osti_6952012,
title = {Tunneling of hydrogen between molecules in solution},
author = {Schmidt, P P},
abstractNote = {This paper reports a treatment of the tunneling of hydrogen between two molecular centers in a system dissolved in a simple liquid. The purpose is to see whether spectroscopic signatures of the tunneling persist in the form of splittings of the vibrational modes. The analysis uses realistic potential energy functions for the interaction between hydrogen and its molecular skeleton. The effect of the liquid is modeled with Lennard-Jones potentials and is handled in the Born-Oppenheimer limit with the Metropolis/Monte Carlo algorithm. The calculations simulate the effect of solvent pair potentials and temperature on the splittings due to light atom tunneling. The analysis is general and should be useful for fairly complicated molecular systems. For the simple generic system considered, A-H + B {leftrightarrow} A + H-B in an argon-like solvent, observable inhomogeneous broadening can arise due to the environment. Values for the parameters in the A-H Morse potential were chosen to yield values for the splittings in the ground and excited states that were near to those found for the ammonial inversion. In liquid argon, the transitions and the associated splittings were shifted were shifted considerably when compared to the vacuum values. Moreover, there was considerable broadening. The splitting did, however, persist; thus, for the system examined, a spectroscopic signature of the tunneling persists and should be observable.},
doi = {10.1021/j100355a008},
url = {https://www.osti.gov/biblio/6952012}, journal = {Journal of Physical Chemistry; (USA)},
issn = {0022-3654},
number = 18,
volume = 93:18,
place = {United States},
year = {Thu Sep 07 00:00:00 EDT 1989},
month = {Thu Sep 07 00:00:00 EDT 1989}
}