Conformer-specific geminate recombination following methyl nitrite photolysis in solution

Philip M. Coulter, Michael P. Grubb, Andrew J. Orr-Ewing

Research output: Contribution to journalArticle (Academic Journal)

2 Citations (Scopus)
251 Downloads (Pure)

Abstract

The dynamics of the ultraviolet (UV) photoexcitation of methyl nitrite in weakly interacting perfluoromethylcyclohexane solution are investigated using transient absorption spectroscopy. UV excitation in the structured S1 ← S0 absorption band induces dissociation, with geminate recombination and vibrational cooling of syn and anti-conformers of methyl nitrate on a timescale of ∼56 ps. Solvent-induced vibrational cooling favours relaxation to the higher-energy anti-conformer on entropic grounds, and subsequent inter-conversion to the lower-energy syn-conformer is prevented by a 3500 cm–1 barrier. UV excitation to the S2S2 state produces a transient electronic absorption band resembling the absorption spectrum of NO2.
Original languageEnglish
Pages (from-to)416-420
Number of pages5
JournalChemical Physics Letters
Volume683
Early online date1 Feb 2017
DOIs
Publication statusPublished - 1 Sep 2017

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