Open AccessUnimolecular reaction dynamics of well characterized ionic reactions. Final report, 1993--1997
Author(s) -
Tomas Baer
Publication year - 1997
Language(s) - English
Resource type - Reports
DOI - 10.2172/290882
Subject(s) - chemistry , dissociation (chemistry) , rrkm theory , isomerization , ionic bonding , reaction coordinate , transition state theory , transition state , ion , ab initio , reaction dynamics , computational chemistry , radical , dimer , molecular dynamics , chemical physics , photochemistry , reaction rate constant , kinetics , molecule , organic chemistry , physics , quantum mechanics , catalysis
The dissociation dynamics of well characterized and energy selected ions have been investigated by photoelectron photoion coincidence (PEPICO) spectrometry. A number of ions have been found which dissociate in competition with isomerization and which thus lead to multi-component decay rates. The dissociation dynamics on such complex potential energy surfaces are common for many free radical reactions, including some of importance to combustion processes. Individual reaction rates for isomerization and dissociation have been extracted from the data. In addition, all rates have been successfully modeled with the RRKM theory in combination with ab initio molecular orbital calculations. The dissociation dynamics of a dimer ion system has been studied on the UNC PEPICO apparatus as well as at the Chemical Dynamics Beam line of the ALS. This proof of principle experiment shows that it is possible to investigate such systems and to determine the heats of formation of free radicals by this approach. Finally, a dissociation involving a loose transition state with no exit barrier has been successfully modeled with a simplified version of the variational transition state theory (VTST). The aim of all of these studies is to develop protocols for modeling moderately complex unimolecular reactions with simple models