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 (~14 500 cm-1) were identified. A structural determination by isotopic substitution and a hyperfine analysis of the Ar-Si17O 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°. 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° 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 Ka = ±1 levels for Ar-28SiO, suggesting that the present theoretical treatment well reproduces the salient properties of the intramolecular potential.
M. C. McCarthy et al., "The Rotational Spectrum and Potential Energy Surface of the Ar-SiO Complex," Journal of Chemical Physics, vol. 149, no. 13, American Institute of Physics (AIP), Oct 2018.
The definitive version is available at https://doi.org/10.1063/1.5048202
Center for High Performance Computing Research
Keywords and Phrases
Crystal Atomic Structure; Geometry; Ground State; Isotopes; Microwave Spectroscopy; Molecular Physics; Potential Energy; Potential Energy Surfaces; Quantum Chemistry; Rate Constants; Silicon Oxides; Spectral Resolution, Equilibrium Structures; Fourier Transform Microwave Spectroscopy; High Spectral Resolution; Intramolecular Potential; Structural Determination; Theoretical Treatments; Transition Frequencies; Vibrationally Excited State, Silicon Compounds
International Standard Serial Number (ISSN)
Article - Journal
© 2018 The Authors, All rights reserved.
01 Oct 2018