Which way did it go? Revisiting the time-resolved study of bromine atom and iodine molecule

The low collision energy interaction of Br($\rm\sp 2P\sb {3/2}$) (Br) or Br($\rm\sp 2P\sb {1/2}$)(Br$\sp {*}$) and I$\sb 2$ is studied in real time. The method of detection, Resonance Enhanced Multiphoton Ionization (REMPI)-Time of Flight Mass Spectroscopy (TOFMS), allows unambiguous identification of products. The interaction is initiated in a restricted region of phase space defined by the geometry of the precursor dimer, H(D)Br$\rm\sp {*}I\sb 2$. The photodissociation of H(D)Br provides both Br and Br$\sp {*}$. The combination of low collision energy and narrow distribution of initial conditions results in a metastable intermediate complex, $\rm I\sb 2Br\sp {*}$. We simultaneously detect two transients, one of which is consistent with the above mentioned complex undergoing an internal conversion to either the ground or 1$\rm\sp {st}$ excited state. The second transient may contain a contribution from the ground state reaction, Br+I$\sb 2$, but interference from other channels makes this transient difficult to assign. Both transients' risetimes vary as a function of precursor constitution, i.e. H(D)Br$\rm\sp {*}I\sb 2$, a feature that is readily explained by a simple 1$\rm\sp {st}$ order kinetic model.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2011

Author dc:creator

• Tuchler, Matthew Frederick

Contributors dc:contributor

• McDonald, J. Douglas

• Chemistry, Physical

Statement dc:rights

• Copyright 1995 Tuchler, Matthew Frederick

Language dc:language

eng

Identifier

AAI9624521
(UMI)AAI9624521

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/22275