Photoelectron Spectroscopy of Chloro-Substituted Phenylnitrene Anions

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 113; no. 34; pp. 9467 - 9473
• Main Authors: Wijeratne, Neloni R, Fonte, Maria Da, Ronemus, Alan, Wyss, Phillip J, Tahmassebi, Daryoush, Wenthold, Paul G
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 27.08.2009
• Subjects: A: Kinetics, Spectroscopy
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp9039594

The 355 nm time-of-flight negative ion photoelectron spectra of (o-, m-, and p-chlorophenyl)nitrene radical anions are reported. Electron affinities are obtained from the photoelectron spectra, and are 1.79 ± 0.05, 1.82 ± 0.05, and 1.72 ± 0.05 eV for the (o-, m-, and p-chlorophenyl)nitrenes, respectively. Singlet−triplet splittings are determined to be 14 ± 2, 15 ± 1, and 14 ± 2 kcal/mol, respectively. The shapes of the photoelectron bands indicate resonance interactions in the singlet states for the ortho- and para-substituted isomers, which is attributed to quinoidal structures of the open-shell singlet states. Reanalysis of the photoelectron spectrum of phenylnitrene anion leads to a revised experimental singlet−triplet splitting of 14.8 kcal/mol in the unsubstituted phenylnitrene.