The rotational spectrum and potential energy surface of the Ar-SiO complex

摘要

The rotational spectra of five isotopic species of the Ar-SiO complex have been observed at high-spectral resolution between 8 and 18 GHz using chirped Fourier transform microwave spectroscopy and a discharge nozzle source; follow-up cavity measurements have extended these measurements to as high as 35 GHz. The spectrum of the normal species is dominated by an intense progression of a-type rotational transitions arising from increasing quanta in the Si-O stretch, in which lines up to v = 12 (similar to 14 500 cm(-1)) were identified. A structural determination by isotopic substitution and a hyperfine analysis of the Ar-(SiO)-O-17 spectrum both suggest that the complex is a highly fluxional prolate symmetric rotor with a vibrationally averaged structure between T-shaped and collinear in which the oxygen atom lies closer to argon than the silicon atom, much like Ar-CO. To complement the experimental studies, a full dimensional potential and a series of effective vibrationally averaged, two-dimensional potential energy surfaces of Ar + SiO have been computed at the CCSD(T)-F12b/CBS level of theory. The equilibrium structure of Ar-SiO is predicted to be T-shaped with a well depth of 152 cm(-1), but the linear geometry is also a minimum, and the potential energy surface has a long, flat channel between 140 and 180 degrees. Because the barrier between the two wells is calculated to be small (of order 5 cm(-1)) and well below the zero-point energy, the vibrationally averaged wavefunction is delocalized over nearly 100 degrees of angular freedom. For this reason, Ar-SiO should exhibit large amplitude zero-point motion, in which the vibrationally excited states can be viewed as resonances with long lifetimes. Calculations of the rovibrational level pattern agree to within 2% with the transition frequencies of normal and isotopic ground state Ar-SiO, and the putative K-a = +/- 1 levels for Ar-(SiO)-Si-28, suggesting that the present theoretical treatment well reproduces the s