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Structure and Decay of Gaseous Organic Radical Cations Studied by Their Radiative Decay, Exemplified by the 1,3‐Pentadiyne Cation
Author(s) -
Maier John P.
Publication year - 1981
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.198106381
Subject(s) - radiative transfer , chemistry , quantum yield , excited state , atomic physics , radical ion , relaxation (psychology) , fluorescence , emission spectrum , excitation , yield (engineering) , ion , spectral line , photochemistry , materials science , physics , optics , social psychology , psychology , organic chemistry , quantum mechanics , astronomy , metallurgy
The radiative decay of over a hundred open‐shell organic radical cations has now been established. As a result, the spectral structure of such cations in their ground and excited electronic states can be probed with resolutions of the order of ⩽ 1 cm −1 . This is achieved by means of emission and laser‐induced fluorescence techniques. The analysis of the emission and excitation spectra provides the vibrational frequencies of many of the totally symmetric fundamentals of the cations in the two electronic states. In order to study the relaxation behavior of these cations under “isolated conditions”, the lifetimes and fluorescence quantum fields can be obtained by means of photoelectron‐photon coincidence measurements. These data yield the radiative and non‐radiative rate constants as a function of the internal energy of the cations. The structural and decay information obtained from each of these techniques is illustrated using the 1,3‐pentadiyne radical cation as example.