Two-center three-electron bonding in ClNH{sub 3} revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH{sub 3} → ClNH{sub 2} + H reaction
- Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)
- Department of Physical Chemistry II, Ruhr-University Bochum, D-44801 Bochum (Germany)
Pyrolytic dissociation of Cl{sub 2} is employed to dope helium droplets with single Cl atoms. Sequential addition of NH{sub 3} to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH{sub 3} → ClNH{sub 2} + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C{sub 3v} symmetric top. Frequency shifts from NH{sub 3} and dipole moment measurements are consistent with a ClNH{sub 3} complex containing a relatively strong two-center three-electron (2c–3e) bond. The nature of the 2c–3e bonding in ClNH{sub 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 in experimental spectra of two other complexes, NH{sub 3}Cl and Cl–HNH{sub 2}, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH{sub 3} → HCl + NH{sub 2}.
- OSTI ID:
- 22657932
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 16 Vol. 144; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Correction: Spectroscopic observation of two-center three-electron bonded (hemi-bonded) structures of (H 2 S) n + clusters in the gas phase
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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)
|
journal | January 2019 |
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