Reaction of the C{sub 3}(X{sup 1}Σ{sub g}{sup +}) carbon cluster with H{sub 2}S(X{sup 1}A{sub 1}), hydrogen sulfide: Photon-induced formation of C{sub 3}S, tricarbon sulfur
Journal Article
·
· Journal of Chemical Physics
- Department of Chemistry and Center for Chemical Physics, University of Florida, P.O. Box 117200, Gainesville, Florida 32611-7200 (United States)
In this paper we report on the neutral-neutral reaction of the C{sub 3} carbon cluster with H{sub 2}S in solid inert argon at 12 K, conditions that mimic, in part, the surfaces of interstellar grains. In the first step of the reaction, a C{sub 3}•H{sub 2}S complex is formed via an almost barrierless entrance addition mechanism. This complex, stabilized by an estimated 7.45 kJ/mol (CCSD(T)/aug-cc-pVTZ//B3LYP/6-311++G(d,p) level), is formed by the interaction of a terminal carbon of C{sub 3} with a hydrogen in H{sub 2}S. This con-covalent complex displays a band at 2044.1 cm{sup −1} observed via Fourier transform infrared absorption spectroscopy. With the help of the MP2/aug-ccpVDZ level method, this band is assigned to the CC asymmetric vibration mode. When the complex is exposed to UV-visible photons (hν < 5.5 eV) the tricarbon sulfur C{sub 3}S molecule is identified, based on the appearance of a characteristic CC stretching band at 2047.5 cm{sup −1}. Calculated ground-state potential energy surfaces also confirm the concomitant formation of molecular H{sub 2}. This facile reaction pathway involves an attainable transition state of 174.4 kJ/mol. Conversely, competing lower-energy reaction pathways that would lead to the generation of H{sub 2}C{sub 3}S (propadienethione), or C{sub 2}H{sub 2} (acetylene) and CS, involve much more complex, multi-stage pathways, and are not observed experimentally.
- OSTI ID:
- 22413244
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 20 Vol. 141; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
A Combined Crossed Molecular Beam and Theoretical Investigation of the Elementary Reaction of Tricarbon (C3(X1Σg+)) with Diacetylene (C4H2(X1Σg+)): Gas Phase Formation of the Heptatriynylidyne Radical (l-C7H(X2Π))
The Hidden Path to the Resonance-Stabilized Fulvenallenyl Radical (C7H5) via the Bimolecular Reaction of Tricarbon (C3, X1Σg+) with 1,3-Butadiene (C4H6; X1Ag)
Resolving the kinetics of individual aqueous reaction steps of actinyl (AnO 2 + and AnO 2 2+ ; An=U, Np, and Pu) tricarbonate complexes with ferrous iron and hydrogen sulfide from first principles
Journal Article
·
Mon Apr 21 20:00:00 EDT 2025
· Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
·
OSTI ID:2565572
The Hidden Path to the Resonance-Stabilized Fulvenallenyl Radical (C7H5) via the Bimolecular Reaction of Tricarbon (C3, X1Σg+) with 1,3-Butadiene (C4H6; X1Ag)
Journal Article
·
Wed Jan 28 19:00:00 EST 2026
· Journal of Physical Chemistry Letters
·
OSTI ID:3023804
Resolving the kinetics of individual aqueous reaction steps of actinyl (AnO 2 + and AnO 2 2+ ; An=U, Np, and Pu) tricarbonate complexes with ferrous iron and hydrogen sulfide from first principles
Journal Article
·
Thu Jul 25 00:00:00 EDT 2019
· Radiochimica Acta
·
OSTI ID:1800339