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Title: 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

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 muchmore » more complex, multi-stage pathways, and are not observed experimentally.« less
Authors:
; ; ; ;  [1]
  1. Department of Chemistry and Center for Chemical Physics, University of Florida, P.O. Box 117200, Gainesville, Florida 32611-7200 (United States)
Publication Date:
OSTI Identifier:
22413244
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 20; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; ACETYLENE; ARGON; CARBON; COVALENCE; FOURIER TRANSFORMATION; GROUND STATES; HYDROGEN; HYDROGEN SULFIDES; INTERACTIONS; INTERSTELLAR GRAINS; MOLECULES; PHOTONS; SOLIDS; SULFUR; SURFACES