Geometry changes accompanying electronic excitation of nitrosomethane in the 650 nm region

Nikolaus P. Ernsting, Josef Pfab, Joachim Römelt

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42 Citations (Scopus)


The vapour phase absorption spectrum of nitrosomethane in the 600-720 nm region has been re-examined. The overall complexity of the spectrum is shown to be due to a conformational change from the eclipsed ground state to a staggered excited state. The prominent torsional features have been reassigned and are found to be consistent with a barrier of 500 ± 100 cm-1 to internal rotation in the excited state. Progressions of 390 and 1420 cm -1 have been assigned to the CNO bending and NO stretching modes in the excited state. Only one electronic absorption system with a Franck-Condon forbidden origin at 694.1 nm corresponding to the 1A? ? 1 A' (n-, p*) transition has been observed. The geometry changes accompanying electronic excitation have been estimated using ab initio calculations for the 1 A? state. A substantial lengthening of the CN and NO bonds, a widening of their bond angle and a change in the phase of the torsional barrier are predicted.

Original languageEnglish
Pages (from-to)2286-2294
Number of pages9
JournalJournal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics
Publication statusPublished - 1978


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