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J Chem Theory Comput. 2013 Jun 11;9(6):2697-705. doi: 10.1021/ct400324w. Epub 2013 May 6.

Computational Studies of Bridging Structures and Isomerism in Substituted Disilynes.

Author information

1
EaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife KY16 9ST, Scotland, United Kingdom.
2
Chemistry Department, University of Aberdeen, Meston Walk, Aberdeen, AB24 3UE, Scotland, United Kingdom.

Abstract

The substituted disilyne molecules, Si2Li2 and Si2HX, where X = Li, F, and Cl, have been investigated using the high-level CCSD(T) and CCSD(T)-F12 ab initio methods. The calculations have found or confirmed the existence of several isomeric forms and transition states for each molecule. Optimized geometries, relative energies, and harmonic vibration frequencies are reported. Bridging structures exist in all cases. Comparisons are made with existing literature results for the related Si2H2, C2X2, and C2HX isomerizing systems. Additionally, CCSD(T) and CCSD(T)-F12 calculations were performed for Si2H2, for which experimental spectroscopic data are available. Results calculated with CCSD(T)-F12 and the cc-pVTZ-F12 basis set are of comparable quality as those computed with CCSD(T) and the much larger cc-pV(6+d)Z basis set, at much less computational cost. We recommend the CCSD(T)-F12/cc-pVTZ-F12 level of theory as a very attractive alternative to conventional CCSD(T).

PMID:
26583863
DOI:
10.1021/ct400324w

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