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

Opoku-Agyeman, Bernice

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

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

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

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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