High-Resolution Spectroscopy and Structure of Heavy Carbon Subchalcogenides: Tricarbon Selenide, C3Se.

Abstract

Linear tricarbon selenide, C₃Se, has been studied spectroscopically for the first time using a combination of high-resolution infrared and microwave techniques. Probing laser ablation products from carbon-selenium targets in a free jet expansion with He, initial spectroscopic detection was accomplished in the infrared at a wavelength of 5 μm in search of the ν₁ vibrational fundamental. Along with the band of the most abundant isotopic species C₃⁸⁰Se found centered at about 2039 cm^-1, the corresponding bands of the C₃⁸²Se, C₃⁷⁸Se, C₃⁷⁶Se, and C₃⁷⁷Se isotopologues were also detected. Pure rotational spectra of the five C₃Se isotopologues in the 8-18 GHz frequency range were observed in a supersonic jet expansion using chirped-pulse microwave spectroscopy of the discharge products of selenophene, c-C₄H₄Se. Spectroscopic analyses were guided by results from high-level quantum-chemical calculations carried out at the coupled-cluster level of theory using large correlation-consistent basis sets. Using the experimentally derived ground-state rotational constants of five isotopologues and calculated zero-point vibrational corrections, an accurate semiexperimental equilibrium carbon-selenium bond length is derived.