Measurement of the autoionization lifetime of the superexcited atomic sulfur S(3s23p3(2Do)4d) state using tunable vacuum ultraviolet (VUV) radiation

Abstract

A new method is described that combines a tunable coherent vacuum ultraviolet (VUV) radiation source and an ion velocity imaging apparatus to study the autoionization of superexcited sulfur atoms. The photolysis of CS2 at 193 nm is used to produce metastable sulfur atoms in the 1D2 state. The S(1D2) atom is then directly excited to the neutral superexcited state 3s23p3(2Do)4d (1Do2) at 11.317 eV with a tunable VUV photon at ~121.896 nm. This excited state then undergoes autoionization into the first ionization continuum state of S+(4So3/2) + e–, which is not directly accessible from the S(1D2) state through optical transition. By monitoring the S+ signal in the time-of-flight mass spectrometer while scanning the excitation wavelength, the line profile of the 3s23p34d 1Do2 ← 3s23p4 1D2 transition is recorded and found to have a full width at half maximum (FWHM) of 0.9 cm–1. This has been used to determine an autoionization lifetime of the neutral superexcited 3s23p34d 1Do2 state of 5.9 ps. The accurate measurement of the autoionization lifetime provides a benchmark for testing fundamental theoretical models of processes occurring in excited states of atoms. Key words: autoionization, atomic sulfur, vacuum ultraviolet (VUV), full width at half maximum (FWHM).