Ab initio Study of Some Intramolecularly Donor‐Stabilized Silenes

Abstract

Keywords: Silenes / Ab initio calculations / Donor-acceptor systems Ab initio calculations were performed to predict geometric structures, stabilizing energies and rotational barriers of some intramolecularly donor-stabilized silenes. Calculations were performed using the HF, MP2, and B3LYP method with the 6-31G(d) and 6-31++G(d,p) basis set. Results were compared to experimentally available X-ray structures and energy barriers known from temperature dependent 1 H NMR

Solvation Effects on Self-Association and Segregation Processes in tert-Butanol–Aprotic Solvent Binary Mixtures

“…This is unlike the free-OH components, which are expected to be less involved in intermolecular interactions. More general fitting functions could have been used, combining combination (sum or product) of Gaussian and Lorentzian functions . We have decided to conform to the initially proposed model, in order to be consistent with the underlying ab initio calculations, to limit the number of free parameters, and to allow for a direct comparison with the existing literature assuming the same level of approximations.…”

“…More general fitting functions could have been used, combining combination (sum or product) of Gaussian and Lorentzian functions. 36 We have decided to conform to the initially proposed model, 7 in order to be consistent with the underlying ab initio calculations, 6 to limit the number of free parameters, and to allow for a direct comparison with the existing literature assuming the same level of approximations. In this model, the contribution of each component to the Raman spectra is weighted by the fraction of each n-mer and the Raman scattering activity of the stretching mode considered.…”

Response to “Comment on ‘New statistical mechanical model for calculating Kirkwood factors in self-associating liquid systems and its application to alkanol+cyclohexane mixtures’ ” [J. Chem. Phys. 127, 047101 (2008)]

“…I principally doubt whether such artificially constructed details reflect the real molecular liquid structure of alcohols and mixtures with other solvents. Our quantum mechanical ab initio calculations of alcohol clusters up to six members made on the highest possible level [5][6][7] revealed on enormous variety of structural details and a practically uncountable number of energetic minima, in particular, shallow minima of conformational isomers. Any attempt of involving significant structural details into a statistical thermodynamic theory has in the first place to account for essential features of these results of ab initio calculated cluster formations.…”