Table of Contents
Laser Chemistry
Volume 3, Issue 1-6, Pages 29-47

Multiphoton Ionization Mass Spectrometric (MPIMS) Study of Phenol: Mechanism of Ionic Fragment Formation

1Department of Chemistry, University of California, Los Angeles 90024, California, USA
2Department of Physics, Argonne National Laboratory, Argonne 60439, Ill., USA
3Air Force Geophysics Laboratory, Hanscom Air Force Base, 01731, MA, USA

Copyright © 1983 Hindawi Publishing Corporation. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


Time of flight (TOF) mass spectrometry is used in conjunction with a variable repelling voltage technique to elucidate the mechanism by which phenol ionizes and dissociates under 266 nm pulsed laser irradiation in combination with a 532 nm or 355 nm pulsed laser. The results suggest that, like benzene, the molecular ion is the predominant precursor of all ionic species generated in the process. Predominance of C5Hx+ species at relatively low powers confirms the presence of a low energy dissociation channel involving the elimination of CO. The use of a second laser at 532 nm is found to selectively destroy the C5Hx+ (as compared to the parent ion) species. The parent ion is found to be protected from the radiation of the second laser pulse at 532 nm but not at 355 nm if the second laser pulse is delayed by 50 ns. This is explained in terms of relaxation within the parent ion energy levels, the location of a low energy dissociation channel and the wavelengths of the lasers used. The main aspects of the fragmentation pattern are discussed in terms of the statistical theory of Rebentrost and Ben-Shaul.