Carbon–sulfur chains: A high‐resolution infrared and quantum‐chemical study of C₃S and SC₇S

Abstract

In the course of a 5 μm high‐resolution infrared study of laser ablation products from carbon–sulfur targets, the ν1 vibrational mode region of linear C3S has been studied continuously from 2046 to 2065 cm−1. Besides the prominent vibrational fundamental, the region was found to feature the ν1+ν5−ν5, ν1+ν4−ν4, and even ν1+ν3−ν3 hot bands, the latter two of which were observed for the first time. Owing to the high signal‐to‐noise ratio obtained, the ν1 mode of C334S could also be observed in natural abundance for the first time at high spectral resolution in the infrared. At 2061 cm−1, hidden inside the R−branch of the C3S ν1 fundamental mode, a weak new band is observed which exhibits very tight line spacing and stems from a heavy both carbon and sulfur containing carrier. On the basis of high‐level quantum‐chemical calculations of selected carbon–sulfur chains and other carbon‐rich cumulenes, this feature is attributed to the ν5 vibrational fundamental of linear SC7S, which stands for the first gas‐phase spectroscopic detection of this long cumulenic chain.

Vibrational satellites of C2S, C3S, and C4S: microwave spectral taxonomy as a stepping stone to the millimeter-wave band

“…, and (v 1 , v 3 ) = (1, 1) have also been observed for the first time in the centimeter domain using previously reported spectroscopic constants for these states 38,39 , see Table A8.…”

“…37. d Centimeter-wave lines observed for the first time, using rotational constants determined from previous works [38][39][40] . See Tables A8 and A15 for a complete listing of observed transitions.…”

Experimental and quantum-chemical characterization of heavy carbon subchalcogenides: Infrared detection of SeC$_3$Se

“…Carbon-selenium clusters were observed with the same experimental setup used in recent investigations of carbon-sulfur clusters [11,12,14]. Briefly, the spectrometer comprises a laser-ablation source (Nd:YAG laser frequencytripled to operate at a wavelength of 355 nm, a repetition rate of 20 Hz, and a pulse energy of about 20 mJ) for cluster production, a widely tunable quantum cascade laser (QCL, Daylight Solutions) as a monochromatic radiation source and a Herriott-type multireflection cell aligned such to allow for 48 passes of the QCL beam.…”

“…1, 2, and references therein]. Particularly because of the latter, those clusters comprising group 14 and 16 heteroatoms, i.e., oxygen, sulfur, and silicon, have received special attention from some high-resolution spectroscopists [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] and chains as complex as C 5 S have been detected in space [20]. Considerably less is known for clusters containing heavier elements X.…”

Topology of electrostatic potential and electron density reveals a covalent to non-covalent carbon–carbon bond continuum

“…The V(r) values clearly suggest the double bond character exhibited by most of the carbon subsulfides 12 and carbon subchalcogenides. 19,[64][65][66][67][68] Furthermore, the MESP topology study is conducted on anionic, cationic, radical systems and some neutral molecules (Fig. 4) containing multiple type of bonds such as C-C, CQC, CRC, aromatic bonds, etc.…”