Abstract

Abstract This chapter describes the use of negative ion photoelectron spectroscopy (NIPES) for investigating the transition states (TSs) for several organic reactions: (a) ring inversion and bond shifting in cyclooctatetraene, (b) ring opening and ring closure of cyclopropanone via an oxyallyl TS, and (c) fragmentation of triplet cyclopropanetrione [(CO) 3 ] to CO plus triplet ethylenedione (O C C O). The application of NIPES to access the D 3h hilltop for fragmentation of singlet (CO) 3 to three molecules of CO is also described, and the use of NIPES for TS spectroscopy of X + HX ➔ XH + X reactions is discussed.

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