Two-center three-electron bonding in ClNH3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH3 → ClNH2 + H reaction
Abstract
Pyrolytic dissociation of Cl2 is employed to dope helium droplets with single Cl atoms. Sequential addition of NH3 to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH3 → ClNH2 + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C3v symmetric top. Frequency shifts from NH3 and dipole moment measurements are consistent with a ClNH3 complex containing a relatively strong two-center three-electron (2c–3e) bond. The nature of the 2c–3e bonding in ClNH3 is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. As a result, computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH3Cl and Cl–HNH2, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH3 → HCl + NH2.
- Authors:
-
[1]
- Univ. of Georgia, Athens, GA (United States)
- Univ. of New Mexico, Albuquerque, NM (United States)
- Ruhr-Univ. Bochum, Bochum (Germany)
- Publication Date:
- Research Org.:
- Univ. of Georgia, Athens, GA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1409058
- Alternate Identifier(s):
- OSTI ID: 1249677
- Grant/Contract Number:
- SC0008086; FG02-05ER15694; FG02-12ER16298
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 144; Journal Issue: 16; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Moradi, Christopher P., Xie, Changjian, Kaufmann, Matin, Guo, Hua, and Douberly, Gary E. Two-center three-electron bonding in ClNH3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH3 → ClNH2 + H reaction. United States: N. p., 2016.
Web. doi:10.1063/1.4947089.
Moradi, Christopher P., Xie, Changjian, Kaufmann, Matin, Guo, Hua, & Douberly, Gary E. Two-center three-electron bonding in ClNH3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH3 → ClNH2 + H reaction. United States. https://doi.org/10.1063/1.4947089
Moradi, Christopher P., Xie, Changjian, Kaufmann, Matin, Guo, Hua, and Douberly, Gary E. Fri .
"Two-center three-electron bonding in ClNH3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH3 → ClNH2 + H reaction". United States. https://doi.org/10.1063/1.4947089. https://www.osti.gov/servlets/purl/1409058.
@article{osti_1409058,
title = {Two-center three-electron bonding in ClNH3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH3 → ClNH2 + H reaction},
author = {Moradi, Christopher P. and Xie, Changjian and Kaufmann, Matin and Guo, Hua and Douberly, Gary E.},
abstractNote = {Pyrolytic dissociation of Cl2 is employed to dope helium droplets with single Cl atoms. Sequential addition of NH3 to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH3 → ClNH2 + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C3v symmetric top. Frequency shifts from NH3 and dipole moment measurements are consistent with a ClNH3 complex containing a relatively strong two-center three-electron (2c–3e) bond. The nature of the 2c–3e bonding in ClNH3 is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. As a result, computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH3Cl and Cl–HNH2, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH3 → HCl + NH2.},
doi = {10.1063/1.4947089},
journal = {Journal of Chemical Physics},
number = 16,
volume = 144,
place = {United States},
year = {Fri Apr 22 00:00:00 EDT 2016},
month = {Fri Apr 22 00:00:00 EDT 2016}
}
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