Reactive Pathways In The Chlorobenzene-ammonia Dimer Cation Radical: New Insights From Experiment And Theory

Nyambo, Silver

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https://hdl.handle.net/2142/50949 Copy

Description

Title

Reactive Pathways In The Chlorobenzene-ammonia Dimer Cation Radical: New Insights From Experiment And Theory

Author(s)

Nyambo, Silver

Contributor(s)

• Reid, Scott
• Muzangwa, Lloyd
• Kalume, Aimable
• Uhler, Brandon

Issue Date

2014-06-19

Keyword(s)

Clusters/Complexes

Abstract

Previously, we have studied non-covalent interactions in mono-halogenated benzene clusters using mass selected resonant 2-photon ionization methods. We have extended our studies by investigating the interaction between these mono-halobenzenes with a prototypical N atom donor (\chem{NH_3}). Thus, we have obtained electronic spectra of PhX$^{…}$(\chem{NH_3})n ( X=F, Cl, Br and n=1,2….) complexes in the region of the PhX monomer \chem{S_0}-\chem{S_1} ($\pi$$\pi$*) transition. Here we are mainly focusing on PhCl$^{…}$\chem{NH_3} dimer. We found that upon ionization of the dimer, three reactive pathways of the [PhCl$^{…}$\chem{NH_3}]$^{+.}$ have been evidenced. The primary pathway is the Cl atom elimination, previously evidenced. The second and third pathways, HCl elimination and H atom elimination are identified for the first time in the R2PI studies of the dimer. Electronic spectra obtained for the three pathways shows that they originate from a common precursor. The reactive pathways in this system were extensively characterized computationally. We used DFT and post-Hartree Fock electronic structure calculations, Frank-Condon analysis to support our experimental findings. The results were consistent with previous direct ab initio molecular dynamics calculations, we found two nearly iso-energetic Wheland intermediates which lie significantly lower in energy than the initially formed dimer cation radical [PhCl$^{…}$\chem{NH_3}]$^{+.}$.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

Permalink

http://hdl.handle.net/2142/50949

DOI

https://doi.org/10.15278/isms.2014.RB06

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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