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Reaction dynamics of the dichlorocarbene anion using tandem mass spectrometry
Author(s) -
Leyh Bernard,
Mélon Pierre
Publication year - 1993
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210280508
Subject(s) - chemistry , dissociation (chemistry) , ion , excited state , branching fraction , kinetic energy , mass spectrum , mass spectrometry , internal energy , analytical chemistry (journal) , fragmentation (computing) , dichlorocarbene , branching (polymer chemistry) , atomic physics , photochemistry , physics , chromatography , organic chemistry , quantum mechanics , computer science , operating system
The dissociation dynamics of CCl 2 − anions were studied under various internal energy conditions. This study involved the measurement of daughter‐ion spectra and branching ratios and of the amount of kinetic energy released (KER) on the fragments. The competition between C and Cl loss for CCl 2 − ions created by any of the following sequence of processes:was particularly investigated. For process (1), the amount of fragmenting CCl 2 − ions is 8–10 times larger with Kr than with Xe or C 6 H 6 . The KER for Cl loss is smaller than 0.20 eV with the three target gases used. For the loss of C, the KER is much larger (0.7 eV). This KER is, however, equal to 0.21 eV for the collisionally activated C loss in process (2). For this latter process, the C loss vs. Cl loss branching ratio decreases with increasing internal energy. The KERs measured for process (3) are very similar to those obtained for process (1). It is suggested that repulsive or slightly bound excited states which correlate directly to the Cl 2 − ( X 2 Σ u + ) + C asymptote and which are vibronically coupled to the ground state play an important role in these dissociation processes.