TY - JOUR
T1 - Nonradiative transitions and unimolecular dissociation of excited electronic states of ClCN+, BrCN+, and ICN+
AU - Braitbart, O.
AU - Castellucci, E.
AU - Dujardin, G.
AU - Leach, S.
PY - 1985
Y1 - 1985
N2 - Radiative and nonradiative relaxation processes of electronic excited states of ClCN+, BrCN+, and ICN+ formed by He I and Ne I lamp excitation have been studied by photoelectron-photoion and photoion-fluorescence photon (PIFCO) coincidence techniques. The B̃2II states of these ions are found to fluoresce with an intrinsic biexponential decay. The results are interpreted in terms of the small molecule, resonance limit model of radiationless transitions. Average values of the interelectronic state mixing coefficients and coupling matrix elements are determined. Morse function sections of the potential energy surfaces of the X̃2II, Ã2S+, and B̃2II states of the representative ion ClCN+ are calculated and are shown to be propitious for B̃ state relaxation via interelectronic interactions. Dissociative ionization processes of the XCN+ species are also studied, in particular fragmentation into the three channels X+ + CN, CX+ + N, and CN+ + X. Electronically excited CN radicals are detected in He I excited dissociative ionization of BrCN and ICN.
AB - Radiative and nonradiative relaxation processes of electronic excited states of ClCN+, BrCN+, and ICN+ formed by He I and Ne I lamp excitation have been studied by photoelectron-photoion and photoion-fluorescence photon (PIFCO) coincidence techniques. The B̃2II states of these ions are found to fluoresce with an intrinsic biexponential decay. The results are interpreted in terms of the small molecule, resonance limit model of radiationless transitions. Average values of the interelectronic state mixing coefficients and coupling matrix elements are determined. Morse function sections of the potential energy surfaces of the X̃2II, Ã2S+, and B̃2II states of the representative ion ClCN+ are calculated and are shown to be propitious for B̃ state relaxation via interelectronic interactions. Dissociative ionization processes of the XCN+ species are also studied, in particular fragmentation into the three channels X+ + CN, CX+ + N, and CN+ + X. Electronically excited CN radicals are detected in He I excited dissociative ionization of BrCN and ICN.
UR - http://www.scopus.com/inward/record.url?scp=0009984774&partnerID=8YFLogxK
U2 - 10.1021/j100261a018
DO - 10.1021/j100261a018
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AN - SCOPUS:0009984774
SN - 0022-3654
VL - 89
SP - 3252
EP - 3260
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
IS - 15
ER -