Non-adiabatic dynamics of ICN–(AR)N and BRCN–(AR)N

Opoku-Agyeman, Bernice

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https://hdl.handle.net/2142/91392 Copy

Description

Title

Non-adiabatic dynamics of ICN–(AR)N and BRCN–(AR)N

Author(s)

Opoku-Agyeman, Bernice

Contributor(s)

McCoy, Anne B.

Issue Date

2016-06-24

Keyword(s)

Dynamics and kinetics

Abstract

We investigate the dynamics of the photodissociation of ICN$^{–}$(Ar)$_{n}$ and BrCN$^{–}$(Ar)$_{n}$ following electronic excitation to states that dissociate into X$^{–}$ + CN and X$^{}$ + CN$^{–}$ (X = I or Br) using classical dynamics approaches. Observations made from previous experiments and calculations of these anions demonstrated that non-adiabatic effects are important in the photodissociation process and are reflected in the branching ratios of the photoproducts.\footnote{S. Case, E. M. Miller, J. P. Martin, Y. J. Lu, L. Sheps, A. B. McCoy, and W. C. Lineberger, Angew. Chem., Int. Ed. 51, 2651 (2012).}$^{,}$\footnote{B. Opoku-Agyeman, A. S. Case, J. H. Lehman, W. Carl Lineberger and A. B. McCoy, J. Chem Phys. 141, 084305 (2014).} The addition of an argon atom is expected to shift the relative energies of these excited states, thereby altering the product branching. Interestingly, experimental studies show that electronically exciting ICN$^{–}$ solvated with even a single argon atom leads to a small fraction of the products recombine to form ICN$^{–}$.$^{a}$ In this study, the dynamics are carried out using classical mechanics, treating the non-adiabatic effect with a surface hopping algorithm.\footnote{J. C. Tully, J. Chem Phys. 93, 1061 (1990).} We assess the accuracy of this approach by first calculating the branching ratios for the bare anions and comparing the results to those from quantum dynamics calculations.$^{a,b}$ Once the results from both the quantum and classical dynamics are shown to be consistent, the classical dynamics simulations are extended to the argon solvated anions.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

En

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http://hdl.handle.net/2142/91392

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Copyright 2016 by the authors

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