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

Research output: Contribution to journal › Article (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 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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10.1016/j.cplett.2017.01.068

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Coulter, P. M., Grubb, M. P., & Orr-Ewing, A. J. (2017). Conformer-specific geminate recombination following methyl nitrite photolysis in solution. Chemical Physics Letters, 683, 416-420. https://doi.org/10.1016/j.cplett.2017.01.068

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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.",

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

year = "2017",

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

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journal = "Chemical Physics Letters",

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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 -