Performance of Hybrid DFT Compared to MP2 Methods in Calculating Nonlinear Optical Properties of Divinylpyrene Derivative Molecules

Abstract

A series of divinyl-pyrene derivatives of the form D-vinyl-pyrene-vinyl-A, in which D corresponds to an electron donor group and A to an electron acceptor group, were studied in this work. The first purpose was to determine the optimal HF % exchange as incorporated in a range of hybrid functionals (M06HF, M062X, M06L, CAM-B3LYP, PBE0, BMK, and B3LYP) capable to produce, reliably and as close as possible to those obtained from MP2 calculations, NLO parameters and, in particular, first-order static hyperpolarizabilities. The CAM-B3LYP functional was revealed to be the most suitable one. The pair N(CH)/NO was then determined as the most efficient pair of groups in producing appreciable NLO responses. The effect of the substitution position on the pyrene moiety was also investigated, whereby aligning the two substituents involving the D and A groups in the direction of the dipole moment as in the (1,6 DVP) derivatives was shown to be most favorable for increasing the NLO parameters.

Theoretical Investigation of Optical and Nonlinear Optical (NLO) Properties of 3‐Azabenzanthrone Analogues : DFT and TD‐DFT Approach.

“…The more positive charge was observed on 22 C and 18 C due to the diminished electron density in the S 0 . The FMO and MEPS provide the qualitative indication of CT properties Figure . MEP gives an idea about the total charge density present in the molecule which is helpful to identify the molecular polarity.…”

Dissociation of Basic Dyes by Advanced Oxidation: Theoretical Study by DFT Calculations

“…First, we calculated dyes geometries by optimizations performed by the long range corrected version of B3LYP using the coulomb-attenuating method CAM-B3LYP functional 30 combined with the 6-31++G(d, p) basis set in the presence of the solvent water using the solvation model cosmo polarizable continuum model CPCM 31,32 . Knowing that the studied dyes are conjugated and charged systems and their eliminations is done in water solvent, it is for this reason that we have chosen the functional and the base mentioned before because they are more descriptive of the electronic parameters according to previous work [33][34][35][36][37] . The geometries obtained were subjected to single point SP calculations in order to calculate the following parameters: total dipole moments in solution µ tot , hardnesses η, chemical potentials µ, electronegativities χ and solvation Gibbs free energies ∆G solv calculated by SMD solvation model 38 .…”

Experimental and theoretical investigation of linear and nonlinear optical properties of ethyl‐3‐hydroxy‐2‐napthoate azo dyes by solvatochromic, computational aspects, and Z‐scan technique

“…To solve such genuine issues, it is mandatory to use the combination of functionals, which have the different Hartree‐Fock (HF) exchange percentage (%) to find out the proper functional to calculate NLO properties of desired molecule . As the percentage of HF exchange differs in the global hybrid (GH) functionals, which have impact on the validity of that particular functional to estimate the NLO properties . The “GH” functionals, which have a constant “HF” exchange percentage, became very useful as they perform well in electronic structure calculations .…”

“…[60] As the percentage of HF exchange differs in the global hybrid (GH) functionals, which have impact on the validity of that particular functional to estimate the NLO properties. [61] The "GH" functionals, which have a constant "HF" exchange percentage, became very useful as they perform well in electronic structure calculations. [60,62,63] Inspite of vast popularity of GH functionals in the field of quantum chemistry calculations, there are drawbacks due to its exact HF exchange amount, which limits their use to calculate the hyperpolarizability parameters for a range of molecules.…”