IR absorption spectra of aniline cation, anilino radical, and phenylnitrene isolated in solid argon

Electron bombardment of aniline (PhNH₂) in an Ar matrix mainly generated the aniline cation (PhNH₂⁺), anilino (PhNH) and phenyl (Ph) radicals, and phenylnitrene (PhN). Further irradiation of the electron-bombarded matrix sample at 365 nm depleted PhNH₂⁺ and PhN, and resulted in the formation of PhNH₂, PhNH, and Ph. In separate experiments, irradiation of the PhNH₂/Ar matrix samples at 265 or 160 nm mainly generated PhNH and Ph radicals, but without the formation of PhNH₂⁺ and PhN. According to the observed photochemical behaviors, quantum-chemically predicted harmonic vibrational wavenumbers of each species, and the information reported in previous photodissociation studies, we unambiguously characterized the IR features of the aromatic species. The information of the vibrational fundamentals of PhNH is new and the formation mechanism is discussed.