A global potential energy surface and dipole moment surface for silane

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A global potential energy surface and dipole moment surface for silane

Owens, A; Yurchenko, SN; Yachmenev, A; Thiel, W; (2015) A global potential energy surface and dipole moment surface for silane. Journal of Chemical Physics , 143 (24) 10.1063/1.4938563. Green open access

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Abstract

© 2015 AIP Publishing LLC. 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-F12HL, reproduces all four fundamental term values for 28SiH4 with sub-wavenumber accuracy, resulting in an overall root-mean-square error of 0.63 cm-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 ν3 band, and the infrared spectrum for 28SiH4 including states up to J = 20 and vibrational band origins up to 5000 cm-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 DMS for future use.

Type:	Article
Title:	A global potential energy surface and dipole moment surface for silane
Open access status:	An open access version is available from UCL Discovery
DOI:	10.1063/1.4938563
Publisher version:	http://dx.doi.org/10.1063/1.4938563
Language:	English
Additional information:	Copyright 2015 AIP Publishing. This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in Owens, A; Yurchenko, SN; Yachmenev, A; Thiel, W; (2015) A global potential energy surface and dipole moment surface for silane. Journal of Chemical Physics , 143 (24) 10.1063/1.4938563 and may be found at http://dx.doi.org/10.1063/1.4938563
UCL classification:	UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy
URI:	https://discovery.ucl.ac.uk/id/eprint/1474687