Issue 54, 2021

Photoelectron photofragment coincidence spectroscopy of carboxylates

Abstract

Photoelectron–photofragment coincidence (PPC) spectroscopy is a powerful technique for studying the decarboxylation dynamics of carboxyl radicals. Measurement of photoelectron and photofragment kinetic energies in coincidence provides a kinematically complete measure of the dissociative photodetachment (DPD) dynamics of carboxylate anions. PPC spectroscopy studies of methanoate, ethanoate, propanoate, 2-butenoate, benzoate, p-coumarate and the oxalate monoanion are reviewed. All of the systems studied undergo decarboxylation via a two-body DPD channel i.e. Image ID:d1ra06340e-t1.gif, driven by the thermodynamic stability of CO2. Additionally, decarboxylation is observed via a three-body ionic photodissociation channel for p-coumarate. In some cases photodetachment also results in a stable carboxyl radical (RCO2). The branching ratio for DPD, the threshold detachment energy and the peak of the kinetic energy release spectrum are compared for different carboxylates, as a probe of the character of the potential energy landscape in the Franck–Condon region.

Graphical abstract: Photoelectron photofragment coincidence spectroscopy of carboxylates

Supplementary files

Article information

Article type
Review Article
Submitted
21 aug 2021
Accepted
06 okt 2021
First published
22 okt 2021
This article is Open Access
Creative Commons BY-NC license

RSC Adv., 2021,11, 34250-34261

Photoelectron photofragment coincidence spectroscopy of carboxylates

J. A. Gibbard and R. E. Continetti, RSC Adv., 2021, 11, 34250 DOI: 10.1039/D1RA06340E

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