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Title: A global potential energy surface and dipole moment surface for silane

A new nine-dimensional potential energy surface (PES) and dipole moment surface (DMS) for silane have been generated using high-level ab initio theory. The PES, CBS-F12{sup HL}, reproduces all four fundamental term values for {sup 28}SiH{sub 4} with sub-wavenumber accuracy, resulting in an overall root-mean-square error of 0.63 cm{sup −1}. The PES is based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit, and incorporates a range of higher-level additive energy corrections to account for core-valence electron correlation, higher-order coupled cluster terms, and scalar relativistic effects. Systematic errors in computed intra-band rotational energy levels are reduced by empirically refining the equilibrium geometry. The resultant Si–H bond length is in excellent agreement with previous experimental and theoretical values. Vibrational transition moments, absolute line intensities of the ν{sub 3} band, and the infrared spectrum for {sup 28}SiH{sub 4} including states up to J = 20 and vibrational band origins up to 5000 cm{sup −1} are calculated and compared with available experimental results. The DMS tends to marginally overestimate the strength of line intensities. Despite this, band shape and structure across the spectrum are well reproduced and show good agreement with experiment. We thus recommend the PES and DMSmore » for future use.« less
Authors:
 [1] ;  [2] ; ;  [3] ;  [1]
  1. Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany)
  2. (United Kingdom)
  3. Department of Physics and Astronomy, University College London, Gower Street, WC1E 6BT London (United Kingdom)
Publication Date:
OSTI Identifier:
22493416
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 24; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BOND LENGTHS; COMPARATIVE EVALUATIONS; CORRECTIONS; CORRELATIONS; DIPOLE MOMENTS; ELECTRONS; EQUILIBRIUM; EXTRAPOLATION; INFRARED SPECTRA; POTENTIAL ENERGY; RELATIVISTIC RANGE; SILANES; SURFACES; VALENCE; VIBRATIONAL STATES