University of Illinois Urbana-Champaign

Theoretical Investigation Of The Uv-vis Photodissociation Dynamics Of Arn(brcn−)

Opoku-Agyeman, Bernice

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WH14_Abstract.pdf
WH14_Abstract.txt
WH14_Presentation.pptx

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https://hdl.handle.net/2142/50816

Description

Title
Theoretical Investigation Of The Uv-vis Photodissociation Dynamics Of Arn(brcn−)
Author(s)
Opoku-Agyeman, Bernice
Contributor(s)
  • McCoy, Anne B.
  • Lineberger, Carl
  • Case, Amanda
  • Lehman, Julia H
Issue Date
2014-06-18
Keyword(s)
Mini-symposium: Spectroscopy in Kinetics and Dynamics
Date of Ingest
  • 2014-09-17T16:55:02Z
  • 2015-04-14T18:40:56Z
Abstract
We present the results of quantum dynamics studies of photodissociation of BrCN$^{-}$ following electronic excitation to states that dissociate to Br$^{-}$ + CN and Br* + CN$^{-}$. The electronic structure of BrCN$^{-}$ was evaluated with MRCI-SO/aug-cc-pVTZ at a fixed CN distance of 1.18 $\AA$. The calculations were used to evaluate the two-dimensional potential surfaces for the ground and excited states as functions of the Br-CN(center of mass) distances, R, and angles, $\theta$, between CN and R. A diabatic model developed for the two relevant excited states shows a dramatic change in the electronic character of the states near the BrCN$^{-}$ geometry when $\theta\le\pi$/2. The quantum dynamics studies on the bare BrCN$^{-}$ were carried out by exciting wave packets of six vibrational states of BrCN$^{-}$ that are thermally populated at 150K onto each of the two excited states. Upon excitations of the wave packets onto the state accessible in the visible region, 51$\%$ Br$^{-}$ and 49$\%$ CN$^{-}$ photoproducts were calculated. Similar calculations in the UV region yielded 56$\%$ Br$^{-}$ and 44$\%$ CN$^{-}$ photoproducts. Experimentally, when BrCN$^{-}$ is excited in the visible region, 60$\%$ Br$^{-}$ and 40$\%$ CN$^{-}$ photoproducts are obtained while 80$\%$ Br$^{-}$ and 20$\%$ CN$^{-}$ yields were obtained in the UV region. Further dynamics studies of BrCN$^{-}$ solvated in argon will be carried out with varying Ar$_{n}$(BrCN$^{-}$) cluster sizes.
Publisher
International Symposium on Molecular Spectroscopy
Type of Resource
text
Genre of Resource
Conference Paper / Presentation
Language
English
Permalink
http://hdl.handle.net/2142/50816
DOI
https://doi.org/10.15278/isms.2014.WH14
Copyright and License Information
Copyright 2014 by the authors. Licensed under a Creative Commons Attribution 4.0 International License. http://creativecommons.org/licenses/by/4.0/

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Abstracts & Presentations - 2014 International Symposium on Molecular Spectroscopy PRIMARY