University of Illinois Urbana-Champaign

Two-center three-electron bonding in clnh3 revealed via helium droplet infrared spectroscopy: entrance channel complex along the CL + NH3 → CLNH2 + H reaction

Franke, Peter R.

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2105.pdf
772535.pptx

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https://hdl.handle.net/2142/91481

Description

Title
Two-center three-electron bonding in clnh3 revealed via helium droplet infrared spectroscopy: entrance channel complex along the CL + NH3 → CLNH2 + H reaction
Author(s)
Franke, Peter R.
Contributor(s)
  • Douberly, Gary E.
  • Guo, Hua
  • Xie, Changjian
  • Kaufmann, Matin
  • Moradi, Christopher P.
Issue Date
2016-06-23
Keyword(s)
Radicals
Date of Ingest
2017-01-26T21:37:31Z
Abstract
Pyrolytic dissociation of Cl$_{2}$ is employed to dope helium droplets with single Cl atoms. Sequential addition of NH$_{3}$ to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction, Cl + NH$_{3}$ $\rightarrow$ ClNH$_{2}$ + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C$_{3v}$ symmetric top. Frequency shifts from NH$_{3}$ and dipole moment measurements are consistent with a ClNH$_{3}$ complex containing a relatively strong two-center three-electron (2c-3e) bond. The nature of the 2c-3e bonding in ClNH$_{3}$ is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence of two other complexes, NH$_{3}$Cl and Cl-HNH$_{2}$, which are predicted in the entry valley to the hydrogen abstraction reaction, Cl + NH$_{3}$ $\rightarrow$ HCl + NH$_{2}$
Publisher
International Symposium on Molecular Spectroscopy
Type of Resource
text
Genre of Resource
Conference Paper / Presentation
Language
En
Permalink
http://hdl.handle.net/2142/91481
Copyright and License Information
Copyright 2016 by the authors

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Abstracts & Presentations - 2016 International Symposium on Molecular Spectroscopy PRIMARY