Photoelectron Spectroscopy using Pulsed Free Jets

Abstract

The use of pulsed gaseous free jets in the study of atomic and molecular species by ultraviolet photoelectron spectroscopy (UPS) offers a number of advantages over the usual continuous flow room temperature technique. Pulsed free jet expansions provide, on the one hand, 'cold' molecules for which spectroscopy is simplified through the absence of hot band structure and, on the other hand, cluster species including dimers, trimers and higher clusters, as well as intermolecular species, all generally of low intermolecular binding energies. Furthermore a high pressure gas pulse is a suitable medium for the preparation, relaxation and transport of reactive species formed in processes such as pyrolysis, photodissociation or electrical discharge. This paper describes the modifications made to an ultraviolet photoelectron spectrometer to allow measurements on pulsed free jet expansions. The important features of the modified instrument concern the control of the gas beam and the timing electronics for photoelectron detection. Examples of He I photoelectron spectra presented include (a) the demonstration of hot band structure in the room temperature UPS of ammonia, (b) the preparation of the dimer (NOh and higher clusters (NO) n of nitric oxide, (c) the UPS of sulfur dioxide clusters (S02) n' and (d) the UPS of ammonia clusters (NH 3) n'