PNNL

Abstract

The photolysis of pyrrole has been studied in a molecular beam at wavelengths 250 nm, 240 nm and 193.3 nm, using 2 different carrier gases, He and Xe. A broad bimodal distribution of H atom fragment velocities has been observed at all wavelengths. Near threshold at both 240 and 250 nm, , sharp features have been observed in the fast part of the H-atom distribution. Under appropriate molecular beam conditions, these sharp features and the photolysis of pyrrole at both 240 and 250 nm disappear when using Xe as opposed to He as the carrier gas. We attribute this phenomenon to cluster formation between Xe and pyrrole, and this assumption is supported by observation of resonance enhanced multiphoton ionization spectra for the (Xe…pyrrole) cluster followed by photofragmentation of the nascent cation cluster. Ab initio calculations are performed to support the experimental data. Part of this work is supported by the transfer of knowledge program SOUTHERN DYNAMICS MTKD-CT-2004-014306. The experimental work was performed at the Ultraviolet Laser Facility operating at IESL-FORTH and has been supported in part by the European Commission through the Research Infrastructures activity of FP6 (“Laserlab- Europe” RII3-CT-2003-506350). We also wish to thank the graduate program Applied Molecular Spectroscopy (EPEAEK). Part of this work was supported by the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences, US Department of Energy with Battelle Memorial Institute, which operates the Pacific Northwest National Laboratory. Computer resources were provided by the Office of Science, US Department of Energy.