Skip to content

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
Early online date1 Feb 2017
DateAccepted/In press - 30 Jan 2017
DateE-pub ahead of print - 1 Feb 2017
DatePublished (current) - 1 Sep 2017


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.

Download statistics

No data available



  • Full-text PDF (accepted author manuscript)

    Rights statement: The final published version (version of record) is available online via Elsevier at Please refer to any applicable terms of use of the publisher.

    Accepted author manuscript, 853 KB, PDF-document

    Licence: CC BY-NC-ND


View research connections

Related faculties, schools or groups