THEORETICAL STUDIES OF TIME-RESOLVED PHOTOELECTRON SPECTRA OF IBr$^-$
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Date
2009
Journal Title
Journal ISSN
Volume Title
Publisher
Ohio State University
Abstract
In the present study, we examine the time-resolved photoelectron spectra of IBr$^-$. In the photodetachment studies performed by Sanov and co-workers and Lineberger and co-workers,}, {\bf{2005}}, {\it{122}}, 174305; Leonid Sheps, Elisa M. Miller, and W. C. Lineberger (private communication).} the anionic species, prepared in its electronic ground state ($^2\Sigma_{1/2}^+$), is excited to either its {\it{\~{A}}}$^\prime$ ($^2\Pi_{3/2}$) or {\it{\~{B}}} ($^2\Sigma_{1/2}^+$) excited state, before electron photodetachment and dissociation on the {\it{\~{C}}} ($^1\Pi_1$) or higher-lying excited states of the neutral species, respectively. In this work, we use the electronic structure program {\it{Columbus}} to calculate the six lowest electronic states of IBr$^-$ and the ten lowest $\Sigma$ states of IBr at the MR-SO-CISD/aug-cc-pVDZ level of theory/basis, using relativistic core potentials for I and Br. Experimentally determined electronic states of IBr are also used.}, {\bf{2001}}, {\it{114}}(6), 2629.} Vibrational eigenstates for these electronic states are calculated in a discrete variable representation,}, {\bf{1992}}, {\it{96}}(3), 1982.} and propagation of the thermally populated {\it{\~{X}}}-state vibrational wave functions on either the {\it{\~{A}}}$^\prime$ or {\it{\~{B}}} electronic states of the anion is performed using a Lanczos scheme. We then take time-dependent overlaps between these propagated states and the vibrational eigenstates of the neutral surface. Results for IBr$^-$ show good agreement with the experimental time-resolved spectra. Extensions to IBr$^-$(CO$_2$)$_n$ ($n < 2$) will also be discussed.
Description
R. Mabbs, K. Pichugin, and A. Sanov, {\it{J. Chem. Phys.E. Wrede, S. Laubach, S. Schulenburg, A. Brown, E. R. Wouters, A. J. Orr-Ewing, and M. N. R. Ashfold, {\it{J. Chem. Phys.D. T. Colbert and W. H. Miller, {\it{J. Chem. Phys.
Author Institution: Department of Chemistry, The Ohio State University, Columbus, OH 43210
Author Institution: Department of Chemistry, The Ohio State University, Columbus, OH 43210