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) › peer-review

3 Citations (Scopus)

450 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 Sept 2017

Research Groups and Themes

Physical & Theoretical

Access to Document

10.1016/j.cplett.2017.01.068

Full-text PDF (accepted author manuscript)
The final published version (version of record) is available online via Elsevier at http://www.sciencedirect.com/science/article/pii/S0009261417300908. Please refer to any applicable terms of use of the publisher.
Accepted author manuscript, 853 KBLicence: CC BY-NC-ND

Handle.net

Persistent link

Cite this

@article{21c02ec2a5b14dc285b413ea2387c284,

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",

publisher = "Elsevier B.V.",

}

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)

SN - 0009-2614

VL - 683

SP - 416

EP - 420

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

Conformer-specific geminate recombination following methyl nitrite photolysis in solution

Abstract

Research Groups and Themes

Access to Document

Handle.net

Fingerprint

Cite this