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The unimolecular dissociation of ionized tetralin was probed by tandem mass spectrometry, imaging photoelectron photoion coincidence (iPEPICO) spectroscopy and theory. The major reactions observed were the loss of the hydrocarbons CH3•, C2H4 and C3H5• together with H• atom loss. RRKM modeling of the iPEPICO data suggested a two well potential energy surface. Ionized tetralin can lose all four neutrals via H-shift and ring-opening reactions, or CH3• and C2H4 after interconversion to the 1-methylindane ion, a process similar to that found for ionized 1,2-dihydronaphthalene (isomerizing to form the 1-methylindene ion structure). This was confirmed at the B3LYP/6-31+G(d,p) level of theory and potential mechanisms for all reactions are described. The ionization energy of tetralin was established from the threshold photoelectron spectrum to be 8.46 ± 0.01 eV.
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Name: The journal of physical chemistry. A
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