The Lowest-Energy Isomer of C₂Si₂H₄ Is a Bridged Ring: Reinterpretation of the Spectroscopic Data Based on DFT and Coupled-Cluster Calculations

Abstract

The lowest-energy isomer of C 2 Si 2 H 4 is determined by high-accuracy ab initio calculations to be the bridged four-membered ring 1,2-didehydro-1,3-disilabicyclo[1.1.0]butane (1), contrary to prior theoretical and experimental studies favoring the three-member ring silylsilacyclopropenylidene (2). These and eight other low-lying minima on the potential energy surface are characterized and ordered by energy using the CCSD(T) method with complete basis set extrapolation, and the resulting benchmark-quality set of relative isomer energies is used to evaluate the performance of several comparatively inexpensive approaches based on many-body perturbation theory and density functional theory (DFT). Double-hybrid DFT methods are found to provide an exceptional balance of accuracy and efficiency for energy-ordering isomers. Free energy profiles are developed to reason the relatively large abundance of isomer 2 observed in previous measurements. Infrared spectra and photolysis reaction mechanisms are modeled for isomers 1 and 2, providing additional insight about previously reported spectra and photoisomerization channels.

Keywords

• thermoisomerization
• photoisomerization
• organosilicon molecules
• density functional theory
• coupled cluster methods
• Gibbs free energy
• intrinsic reaction coordinate