Femtosecond dynamics of the tert-butyl radical, t-C4H9.

The excited-state dynamics of the tert-butyl radical, t-C4H9, was investigated by femtosecond time-resolved photoionization and photoelectron spectroscopy. The experiments were supported by ab initio calculations. tert-Butyl radicals, generated by flash pyrolysis of azo-tert-butane, were excited into the A 2A1 (3s) state between 347 and 307 nm and the 3p band at 274 and 268 nm and ionized by 810-nm radiation, in a [1 + 2'] or [1 + 3'] process. Electronic structure calculations confirm that the two states are of s and p Rydberg characters, respectively. The carbon framework becomes planar and thus ion-like in both states. The photoelectron spectra are broad and seem to be mediated by accidental intermediate resonances in the probe step. All time-resolved photoelectron spectra can be described by a single decay time. For the A 2A1 state, lifetimes between 180 and 69 fs were measured. Surprisingly, a much longer lifetime of around 2 ps was found for the 3p state. To understand the decay dynamics, the potential energy was computed as a function of several important nuclear coordinates. A [1,2] H-atom shift to the isobutyl radical seems not to be important for the excited-state dynamics. Qualitative considerations indicate curve crossings between the ground state, the 3s state, and a valence state along the asymmetric C-C stretch coordinate that correlates to the dimethylcarbene + methyl product channel. The implications of the present study for earlier work on the nanosecond time scale are discussed.