Steering H-atom diffusion through impurity-doped solid parahydrogen: the role of differential solvation energies

Hinde, Robert

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https://hdl.handle.net/2142/59146 Copy

Description

Title

Steering H-atom diffusion through impurity-doped solid parahydrogen: the role of differential solvation energies

Author(s)

Hinde, Robert

Issue Date

2014-06-19

Keyword(s)

Matrix isolation (and droplets)

Date of Ingest

• 2014-12-08T19:13:07Z
• 2015-04-14T18:41:49Z

Abstract

Ultraviolet irradiation of solid parahydrogen (pH$_2$) matrices doped with suitable H-atom precursor molecules generates H atoms {\it in situ\/} through a series of photoinitiated chemical reactions; these H atoms move through the pH$_2$ matrix through a quantum diffusion process that involves the tunneling-mediated process H + H$_2$ $\rightarrow$ H$_2$ + H. The mobile H atoms may react chemically with other species that are also embedded in the pH$_2$ matrix; an investigation of the kinetics of these H-atom chemical reactions provides us with information about reaction dynamics in the pH$_2$ matrix environment. A recent study of the H + N$_2$O $\rightarrow$ HNNO reaction in solid pH$_2$ [Mutunga, Follett, and Anderson, J. Chem. Phys. {\bf 139}, 151104 (2013)] demonstrates that this reaction exhibits strongly non-Arrhenius behavior, proceeding at measurable rates only when the temperature of the system drops below $T \approx 2.4$ K. A molecular-level understanding of these findings requires information about how the solid pH$_2$ matrix environment affects the long-range entrance channel of the H + N$_2$O reaction. Here, we carry out quantum Monte Carlo simulations of a simple model system (Ar-doped solid pH$_2$) to investigate matrix-induced changes to long-range interactions between H atoms and other impurities embedded in solid pH$_2$ matrices. Our results suggest that the pH$_2$ matrix creates an effective long-range repulsion between the H atom and the Ar impurity, which we explain in terms of differential solvation energies of Ar and H atoms in solid pH$_2$.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Genre of Resource

Conference Paper / Presentation

Language

en

Permalink

http://hdl.handle.net/2142/59146

DOI

https://doi.org/10.15278/isms.2014.RI06

Copyright and License Information

Copyright 2014 by the authors. Licensed under a Creative Commons Attribution 4.0 International License. http://creativecommons.org/licenses/by/4.0/

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