Tunneling of hydrogen between molecules in solution

Journal Article · Thu Sep 07 00:00:00 EDT 1989 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100355a008· OSTI ID:6952012

Schmidt, P P ^[1]

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1. Office of Naval Research, Arlington, VA (USA)

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.

• OSTI ID: 6952012
• Journal Information: Journal of Physical Chemistry; (USA), Vol. 93:18, Issue 18; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

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