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Article
The Rotational Spectrum and Potential Energy Surface of the Ar-SiO Complex
Journal of Chemical Physics
  • Michael C. McCarthy
  • Steve Alexandre Ndengue
  • Richard Dawes, Missouri University of Science and Technology
Abstract

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.

Department(s)
Chemistry
Research Center/Lab(s)
Center for High Performance Computing Research
Comments
The work in Cambridge is supported by NSF Grant Nos. CHE-1058063 and CHE-1566266. R.D. is supported by the US National Science Foundation (No. CHE-1566246).
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
Document Type
Article - Journal
Document Version
Final Version
File Type
text
Language(s)
English
Rights
© 2018 The Authors, All rights reserved.
Publication Date
10-1-2018
Publication Date
01 Oct 2018
Disciplines
Citation Information
Michael C. McCarthy, Steve Alexandre Ndengue and Richard Dawes. "The Rotational Spectrum and Potential Energy Surface of the Ar-SiO Complex" Journal of Chemical Physics Vol. 149 Iss. 13 (2018) ISSN: 0021-9606; 1089-7690
Available at: http://works.bepress.com/richard_dawes/118/