ELECTRONIC ABSORPTION SPECTRUM OF RADIATION-PRODUCED PENTANE AND HEXANE RADICAL CATIONS IN SATURATED CHLOROFLUOROCARBON AND PERFLUOROCARBON MATRICES AT 77 K

Article abstract of DOI:10.1016/S0022-2860(98)80059-8

Pentane and hexane radical cations are produced by irradiation, stabilized in saturated chlorofluorocarbon and perfluorocarbon matrices at 77 K and studied by electronic spectrometry.Special emphasis is laid on the obtainment of pure spectra by suitable deconvolution techniques.Electronic absorption spectra of these cations consist of a broad structureless absorbtion band with maximum at respectively 400 nm (pentane) and 480 nm (hexane).The absorption is intrinsic and is not to a considerable extent affected by the matrix.It is due to transitions from fully-occupied orbitals to the half occupied molecular orbital where the unpaired electron resides.A comparison is made of the electronic absorption spectra with photodissociation spectra obtained by ICR techniques and with theoretical spectra obtained by a conformationally-averaged MINDO/3 approach that includes transition-moment weighting.