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Transient isomers in the photodissociation of bromoiodomethane

Journal article
Authors M. Marcellini
A. Nasedkin
B. Zietz
J. Petersson
J. Vincent
F. Palazzetti
Erik Malmerberg
Q. Y. Kong
M. Wulff
D. van der Spoel
Richard Neutze
J. Davidsson
Published in Journal of Chemical Physics
Volume 148
Issue 13
ISSN 0021-9606
Publication year 2018
Published at Department of Chemistry and Molecular Biology
Language en
Links dx.doi.org/10.1063/1.5005595
Keywords x-ray-scattering, o-h-insertion, naturally produced organohalogens, selective electronic excitation, protein structural dynamics, resonance, raman observation, ultraviolet photolysis, elimination-reactions, reaction pathways, a-band, Chemistry, Physics
Subject categories Physical Sciences, Chemical Sciences

Abstract

The photochemistry of halomethanes is fascinating for the complex cascade reactions toward either the parent or newly synthesized molecules. Here, we address the structural rearrangement of photodissociated CH2IBr in methanol and cyclohexane, probed by time-resolved X-ray scattering in liquid solution. Upon selective laser cleavage of the C-I bond, we follow the reaction cascade of the two geminate geometrical isomers, CH2I-Br and CH2Br-I. Both meta-stable isomers decay on different time scales, mediated by solvent interaction, toward the original parent molecule. We observe the internal rearrangement of CH2Br-I to CH2I-Br in cyclohexane by extending the time window up to 3 mu s. We track the photoproduct kinetics of CH2Br-I in methanol solution where only one isomer is observed. The effect of the polarity of solvent on the geminate recombination pathways is discussed. Published by AIP Publishing.

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