Threshold Photoelectron Spectroscopy of the CHI, CHI, and CI Radicals.

VUV photoionization of the CHI radicals (with = 0, 1, and 2) is investigated by means of synchrotron radiation coupled with a double imaging photoion-photoelectron coincidence spectrometer. Photoionization efficiencies and threshold photoelectron spectra (TPES) for photon energies ranging between 9.2 and 12.

Site-specific hydrogen-atom elimination in photoexcited alkyl radicals.

A prompt site-specific hydrogen-atom elimination from the α-carbon atom (Cα) has been recently reported to occur in the photodissociation of ethyl radicals following excitation at 201 nm [Chicharro et al., Chem. Sci.

Site-specific hydrogen-atom elimination in photoexcited ethyl radical.

The photochemistry of the ethyl radical following excitation to the 3p Rydberg state is investigated in a joint experimental and theoretical study. Velocity map images for hydrogen atoms detected from photoexcited isotopologues CHCH, CHCD and CDCH at ∼201 nm, are discussed along with high-level electronic structure calculations of potential energy curves and non-adiabatic coupling matrix elements (NACME). A novel mechanism governed by a conical intersection allowing prompt site-specific hydrogen-atom elimination is presented and discussed.