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Conformer-specific geminate recombination following methyl nitrite photolysis in solution

Research output: Contribution to journalArticle

Original languageEnglish
Pages (from-to)416-420
Number of pages5
JournalChemical Physics Letters
Volume683
Early online date1 Feb 2017
DOIs
StatePublished - 1 Sep 2017

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.

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