U.S. Department of Energy Office of Scientific and Technical Information
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
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.
Moradi, Christopher P., et al. "Two-center three-electron bonding in ClNH<sub>3</sub> revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH<sub>3</sub> → ClNH<sub>2</sub> + H reaction." Journal of Chemical Physics, vol. 144, no. 16, Apr. 2016. https://doi.org/10.1063/1.4947089
Moradi, Christopher P., Xie, Changjian, Kaufmann, Matin, Guo, Hua, & Douberly, Gary E. (2016). Two-center three-electron bonding in ClNH<sub>3</sub> revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH<sub>3</sub> → ClNH<sub>2</sub> + H reaction. Journal of Chemical Physics, 144(16). https://doi.org/10.1063/1.4947089
Moradi, Christopher P., Xie, Changjian, Kaufmann, Matin, et al., "Two-center three-electron bonding in ClNH<sub>3</sub> revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH<sub>3</sub> → ClNH<sub>2</sub> + H reaction," Journal of Chemical Physics 144, no. 16 (2016), https://doi.org/10.1063/1.4947089
@article{osti_1409058,
author = {Moradi, Christopher P. and Xie, Changjian and Kaufmann, Matin and Guo, Hua and Douberly, Gary E.},
title = {Two-center three-electron bonding in ClNH<sub>3</sub> revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH<sub>3</sub> → ClNH<sub>2</sub> + H reaction},
annote = {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},
url = {https://www.osti.gov/biblio/1409058},
journal = {Journal of Chemical Physics},
issn = {ISSN 0021-9606},
number = {16},
volume = {144},
place = {United States},
publisher = {American Institute of Physics (AIP)},
year = {2016},
month = {04}}
Journal Article
·
Mon Sep 09 00:00:00 EDT 2013
· Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
·OSTI ID:1409049