Gas-Phase Spectroscopic Detection and Structural Elucidation of Carbon-Rich Group 14 Binary Clusters: Linear GeC₃Ge

Abstract

Guided by high-level quantum-chemical calculations at the CCSD(T) level of theory, the first polyatomic germanium-carbon cluster, linear Ge2C3, has been observed at high spectral resolution in the gas phase through its remarkably complex fundamental antisymmetric C-C stretching mode ν3 located at 1932 cm(-1). The observation of a total of six isotopic species permits the derivation of a highly accurate value for the equilibrium Ge-C bond length. The present study suggests that many more Ge-C species might be detectable in the future using a combination of laser-ablation techniques for production and high-resolution infrared and/or microwave techniques for spectroscopic detection.

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

“…As a note of caution it should be mentioned though that for heavy molecules alternative spectroscopic assignments change the rotational constant only little (see e.g., Ref. ). For SC 7 S, changes in quantum number assignment by result in a B 0 change of 0.86 MHz (0.4%) only.…”

“…Prior to the present study, high‐resolution infrared spectroscopic investigations of binary carbon‐rich systems were restricted to clusters comprising up to five atoms only (SC 3 S, SiC 4 , SiC 3 Si, and GeC 3 Ge) . Now that chains as long as SC 7 S have been detected many more and possibly even heavier species might be detectable using the production and detection techniques employed here.…”

“…Carbon-sulfur clusters were observed with an experimental setup similar to the one used in previous investigations of other clusters. [21][22][23][24] Briefly, the spectrometer comprises of a laser-ablation source (Nd:YAG laser frequency-tripled 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. Sample rods were pressed from 3:1 stoichiometric mixtures of graphite and sulfur powder (Sigma-Aldrich) without the necessity to add any kind of glue.…”

Generation and structural characterization of Ge carbides GeCn (n = 4, 5, 6) by laser ablation, broadband rotational spectroscopy, and quantum chemistry

“…The interest in these species is to understand the underlying electronic structure of group 14 elements, and the nature of their chemical bonding. Until recently, only two Ge-species have been observed at high spectral resolution: germanium carbide (GeC) by low-temperature electronic emission 13 , and one symmetric chain, GeC 3 Ge, using infrared free-jet spectroscopy and a laser ablation source 14 . At lower spectral resolution, Graham and coworkers used Fourier transform infrared matrix isolation to measure the vibrational spectra of a number of Ge n C m clusters, including GeC 3 Ge, 15 GeC 5 Ge, 16 and three odd-numbered chains 1-10 | 1 GeC 3 17 , GeC 7 , and GeC 9 .…”

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

“…As far as binary carbon-rich clusters with heavy group 14 elements are concerned, only very recently high-resolution studies of several germaniumbearing clusters have been reported, one infrared observation of nonpolar GeC 3 Ge [2] as well as two Fourier-transform microwave investigations of polar GeC n (n = 2, 4, 5, 6) species [23,24]. The situation is even less favorable with respect to clusters comprising carbon and heavy group 16 elements.…”