Femtosecond dynamics of the 2-methylallyl radical: A computational and experimental study.

We investigate the photodynamics of the 2-methylallyl radical by femtosecond time-resolved photoelectron imaging. The experiments are accompanied by field-induced surface hopping dynamics calculations and the simulation of time-resolved photoelectron intensities and anisotropies, giving insight into the photochemistry and nonradiative relaxation of the radical. 2-methylallyl is excited at 236 nm, 238 nm, and 240.6 nm into a 3p Rydberg state, and the subsequent dynamics is probed by multiphoton ionization using photons of 800 nm. The photoelectron image exhibits a prominent band with considerable anisotropy, which is compatible with the result of theory. The simulations show that the initially excited 3p state is rapidly depopulated to a 3s Rydberg state, from which photoelectrons of high anisotropy are produced. The 3s state then decays within several 100 fs to the D (nπ) state, followed by the deactivation of the D to the electronic ground state on the ps time scale.