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The Electronic Spectrum of the Fulvenallenyl Radical
Author(s) -
Chakraborty Arghya,
Fulara Jan,
Maier John P.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201508961
Subject(s) - chemistry , neon , radical ion , ion , excitation , atomic physics , absorption (acoustics) , absorption spectroscopy , matrix isolation , photochemistry , molecule , materials science , physics , argon , organic chemistry , quantum mechanics , composite material
The fulvenallenyl radical was produced in 6 K neon matrices after mass‐selective deposition of C 7 H 5 − and C 7 H 5 + generated from organic precursors in a hot cathode ion source. Absorption bands commencing at λ=401.3 nm were detected as a result of photodetachment of electrons from the deposited C 7 H 5 − and also by neutralization of C 7 H 5 + in the matrix. The absorption system is assigned to the 1 2 B 1 ←X 2 B 1 transition of the fulvenallenyl radical on the basis of electronic excitation energies calculated with the MS‐CASPT2 method. The vibrational excitation bands detected in the spectrum concur with the structure of the fulvenallenyl radical. Employing DFT calculations, it is found that the fulvenallenyl anion and its radical are the global minima on the potential energy surface among plausible structures of C 7 H 5 .