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

Moradi, Christopher P.; Xie, Changjian; Kaufmann, Matin; Guo, Hua; Douberly, Gary E.

doi:10.1063/1.4947089

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

Journal Article · Fri Apr 22 00:00:00 EDT 2016 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.4947089 · OSTI ID:1409058

Moradi, Christopher P. ^[1]; Xie, Changjian ^[2]; Kaufmann, Matin ^[3]; Guo, Hua ^[2];

^[4]

Univ. of Georgia, Athens, GA (United States); University of Georgia, Athens, GA
Univ. of New Mexico, Albuquerque, NM (United States)
Ruhr-Univ. Bochum, Bochum (Germany)
Univ. of Georgia, Athens, GA (United States)

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 C_3v 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.

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Research Organization:: Univ. of Georgia, Athens, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0008086

OSTI ID:: 1409058

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 16 Vol. 144; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Correction: Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H ₂ S) _n ⁺ clusters in the gas phase Wang, Dandan; Fujii, Asuka Chemical Science, Vol. 9, Issue 15 https://doi.org/10.1039/c8sc90072h	journal	January 2018
Influence of the microsolvation on hemibonded and protonated hydrogen sulfide: infrared spectroscopy of [(H ₂ S) _n (X) ₁ ] ⁺ and H ⁺ (H ₂ S) _n (X) ₁ ( n = 1 and 2, X = water, methanol, and ethanol) Hattori, Keigo; Wang, Dandan; Fujii, Asuka Physical Chemistry Chemical Physics, Vol. 21, Issue 29 https://doi.org/10.1039/c9cp03159f	journal	January 2019

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