Conformer-specific geminate recombination following methyl nitrite photolysis in solution

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

doi:10.1016/j.cplett.2017.01.068

Conformer-specific geminate recombination following methyl nitrite photolysis in solution

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

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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 language	English
Pages (from-to)	416-420
Number of pages	5
Journal	Chemical Physics Letters
Volume	683
Early online date	1 Feb 2017
DOIs	https://doi.org/10.1016/j.cplett.2017.01.068
Publication status	Published - 1 Sep 2017

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title = "Conformer-specific geminate recombination following methyl nitrite photolysis in solution",

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.",

author = "Coulter, {Philip M.} and Grubb, {Michael P.} and Orr-Ewing, {Andrew J.}",

year = "2017",

month = sep,

day = "1",

doi = "10.1016/j.cplett.2017.01.068",

language = "English",

volume = "683",

pages = "416--420",

journal = "Chemical Physics Letters",

issn = "0009-2614",

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TY - JOUR

T1 - Conformer-specific geminate recombination following methyl nitrite photolysis in solution

AU - Coulter, Philip M.

AU - Grubb, Michael P.

AU - Orr-Ewing, Andrew J.

PY - 2017/9/1

Y1 - 2017/9/1

N2 - 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.

AB - 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.

U2 - 10.1016/j.cplett.2017.01.068

DO - 10.1016/j.cplett.2017.01.068

M3 - Article (Academic Journal)

VL - 683

SP - 416

EP - 420

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

ER -

Conformer-specific geminate recombination following methyl nitrite photolysis in solution

Abstract

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