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 |
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Pages (from-to) | 416-420 |
Number of pages | 5 |
Journal | Chemical Physics Letters |
Volume | 683 |
Early online date | 1 Feb 2017 |
DOIs | |
Publication status | Published - 1 Sep 2017 |