Implementation and Optimization of DFT-D/COSab with Respect to Basis Set and Functional: Application to Polar Processes of Furfural Derivatives in Solution

Abstract

The implementation, optimization, and performance of DFT-D, including the effects of solvation, has been tested on applications of polar processes in solution, where dispersion and hydrogen bonding is known to be involved. Solvent effects are included using our ab initio continuum solvation strategy, COSab, a conductor-like continuum solvation model, modified for ab initio in the quantum chemistry program GAMESS. Structure and properties are investigated across various functionals to evaluate their ability to properly model dispersion and solvation effects. The commonly used S22 set with accurate interaction energies of organic complexes has been used for parametrization studies of dispersion parameters and relevant solvation parameters. Dunning's correlation consistent basis sets, cc-pVnZ (n = D, T), are used in the optimization, together with the Grimme B97-D exchange-correlation functional. Both water (ε = 78.4) and ether (ε = 4.33) environments are considered. Optimized semiempirical dispersion correction parameters and solvent extent radii are proposed for several functionals. We find that special parametrization of the semiempirical dispersion correction when used together in the DFT-D/COSab approach is not necessary. The global performance is quite acceptable in terms of chemical accuracy and suggests that this approach is a reliable as well as economical method for evaluation of solvent effects in systems with dispersive interactions. The resulting theory is applied to a group of push-pull pyrrole systems to illustrate the effects of donor/acceptor and solvation on their conformational and energetic properties.

Pressure Catalyzed Bond Dissociation in an Anthracene Cyclophane Photodimer

“…Quantum calculations were utilized to determine the structures and heats of formation of both BA and PI. Calculations were carried out using the Kohn−Shan density functional theory including dispersion (DFT-D), 39 employing a 6-31+G(d) basis set to allow determination of most accurate thermodynamic information for molecules of the size of BA. The dispersion-improved forcefield includes semiempirically corrected noncovalent interactions, which can be significant for aromatic sandwich dimer molecules such as BA.…”

Inter- and Intramolecular Interactions in Triptycene-Derived Bisphosphite Hydroformylation Catalysts: Structures, Energies, and Caveats for DFT-Assisted Ligand Design

“…Today, several DFT variants that include dispersion are available and are recommended . Many benchmark investigations and case studies exist in the literature that claim the superiority of DFT functionals with inclusion of dispersion interactions over those without, − not only in the gas phase but also for systems in solution. − …”

Defined-Sector Explicit Solvent in Continuum Cluster Model for Computational Prediction of pKa: Consideration of Secondary Functionality and Higher Degree of Solvation

“…All calculations were performed with the GAMESS electronic structure program . Full optimizations were carried out including effects of solvation via the DSES-CC model, using B97-D/6-311+G­(2d,p)/COSab, with our most recent implementation of COSab solvation model. − Parameter optimization for several combinations of DFT functional type and basis sets have been carried out within the solvation model in previous work . In our initial development of the DSES-CC model, investigation covering basis set, wave function type, thermodynamic cycle, reaction scheme, and solvent parameters were carried out .…”

“…The present work as well as our previous studies well supports the reliability of the B97-D functional together with a triple-ζ basis set. The dispersion enabled density functional B97-D is a reparameterization of the original B97 hybrid functional of Becke and has been implemented and tested in GAMESS within the solvent model . An ultrafine grid, NRAD = 96 NLEB = 1202 was specified.…”