To Tunnel Or Not To Tunnel, Proton Transfer Is The Question.

Chew, Kathryn

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https://hdl.handle.net/2142/51007 Copy

Description

Title

To Tunnel Or Not To Tunnel, Proton Transfer Is The Question.

Author(s)

Chew, Kathryn

Contributor(s)

• Vaccaro, Patrick
• Nemchick, Deacon

Issue Date

2014-06-18

Keyword(s)

Mini-symposium: Spectroscopy in Kinetics and Dynamics

Abstract

The transduction of protons between donor and acceptor sites, as mediated by the action of adjoining hydrogen bonds, represents one of the most ubiquitous of chemical transformations. While the basic mechanisms underlying such phenomena often can be ascribed to simple acid-base chemistry, the putative roles of selective nuclear and electronic displacements should not be discounted, especially when the presence of a sizeable potential barrier impedes classical hydron-migration pathways. The vibrational and isotopic specificity of hindered intramolecular proton transfer taking place within the ground (\textit{\~{X}$^{1}$}{A}$_{1}$) and the lowest-lying excited (\textit{\~{A}$^{1}$}B$_{2}$ ($\pi ^{*}\pi$) electronic states of the prototypical tropolone (TrOH) system has been probed by implementing multiple-color variants of resonant four-wave mixing (RFWM) spectroscopy, with polarization-resolved detection allowing for the extraction of quantitative rotation-tunneling information. The marked dependence of unimolecular dynamics on the extent and the type of excitation deposited into TrOH internal degrees of freedom will be discussed. Experimentally observed trends and propensities for tunneling-mediated reactivity will be interpreted through use of accompanying quantum-chemical calculations.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

Permalink

http://hdl.handle.net/2142/51007

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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