Universität zu Köln

McGuire, Brett A., Martin-Drumel, Marie-Aline ORCID: 0000-0002-5460-4294, Thorwirth, Sven ORCID: 0000-0001-8200-6710, Bruenken, Sandra, Lattanzi, Valerio, Neill, Justin L., Spezzano, Silvia, Yu, Zhenhong, Zaleski, Daniel P., Remijan, Anthony J., Pate, Brooks H. and McCarthy, Michael C. (2016). Molecular polymorphism: microwave spectra, equilibrium structures, and an astronomical investigation of the HNCS isomeric family. Phys. Chem. Chem. Phys., 18 (32). S. 22693 - 22706. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1463-9084

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Abstract

The rotational spectra of thioisocyanic acid (HNCS), and its three energetic isomers (HSCN, HCNS, and HSNC) have been observed at high spectral resolution by a combination of chirped-pulse and Fabry-Perot Fourier-transform microwave spectroscopy between 6 and 40 GHz in a pulsed-jet discharge expansion. Two isomers, thiofulminic acid (HCNS) and isothiofulminic acid (HSNC), calculated here to be 35-37 kcal mol(-1) less stable than the ground state isomer HNCS, have been detected for the first time. Precise rotational, centrifugal distortion, and nitrogen hyperfine coupling constants have been determined for the normal and rare isotopic species of both molecules; all are in good agreement with theoretical predictions obtained at the coupled cluster level of theory. On the basis of isotopic spectroscopy, precise molecular structures have been derived for all four isomers by correcting experimental rotational constants for the effects of rotation-vibration interaction calculated theoretically. Formation and isomerization pathways have also been investigated; the high abundance of HSCN relative to ground state HNCS, and the detection of strong lines of SH using CH3CN and H2S, suggest that HSCN is preferentially produced by the radical-radical reaction HS + CN. A radio astronomical search for HSCN and its isomers has been undertaken toward the high-mass star-forming region Sgr B2(N) in the Galactic Center with the 100 m Green Bank Telescope. While we find clear evidence for HSCN, only a tentative detection of HNCS is proposed, and there is no indication of HCNS or HSNC at the same rms noise level. HSCN, and tentatively HNCS, displays clear deviations from a single-excitation temperature model, suggesting weak masing may be occurring in some transitions in this source.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code McGuire, Brett A. UNSPECIFIED UNSPECIFIED UNSPECIFIED Martin-Drumel, Marie-Aline UNSPECIFIED orcid.org/0000-0002-5460-4294 UNSPECIFIED Thorwirth, Sven UNSPECIFIED orcid.org/0000-0001-8200-6710 UNSPECIFIED Bruenken, Sandra UNSPECIFIED UNSPECIFIED UNSPECIFIED Lattanzi, Valerio UNSPECIFIED UNSPECIFIED UNSPECIFIED Neill, Justin L. UNSPECIFIED UNSPECIFIED UNSPECIFIED Spezzano, Silvia UNSPECIFIED UNSPECIFIED UNSPECIFIED Yu, Zhenhong UNSPECIFIED UNSPECIFIED UNSPECIFIED Zaleski, Daniel P. UNSPECIFIED UNSPECIFIED UNSPECIFIED Remijan, Anthony J. UNSPECIFIED UNSPECIFIED UNSPECIFIED Pate, Brooks H. UNSPECIFIED UNSPECIFIED UNSPECIFIED McCarthy, Michael C. UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-266233
DOI:	10.1039/c6cp03871a
Journal or Publication Title:	Phys. Chem. Chem. Phys.
Volume:	18
Number:	32
Page Range:	S. 22693 - 22706
Date:	2016
Publisher:	ROYAL SOC CHEMISTRY
Place of Publication:	CAMBRIDGE
ISSN:	1463-9084
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language STATE SPECTROSCOPIC CONSTANTS; GAUSSIAN-BASIS SETS; SAGITTARIUS B2(N); ISOCYANIC ACID; AB-INITIO; INTERSTELLAR-MEDIUM; ISOTHIOCYANIC ACID; ROTATIONAL SPECTRA; ORGANIC-MOLECULES; GALACTIC-CENTER Multiple languages Chemistry, Physical; Physics, Atomic, Molecular & Chemical Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/26623