Investigation of photophysical, structural aspects and nonlinear optical properties of Foron blue SR analogs using Density Functional Theory (DFT)

Abstract

Analogs of 2-[(2Z)-2-[[4-(dihexylamino)-2-methylphenyl]methylidene]-1,1-dioxo-1-benzothiophen-3-ylidene]propanedinitrile (Foron blue SR, Disperse Blue 354) are studied in terms of photophysical, structural aspects and its nonlinear optical properties evaluated by using Density Functional Theory (DFT) and Time Dependent Density Functional Theory (TD-DFT). The structures were optimized by using function B3LYP and basis set used was 6-31G(d). Polarizability (α), first and second order hyperpolarizability (β and γ) was determined by three density functionals B3LYP, CAM-B3LYP and BHandHLYP. B3LYP functional and the basis set 6-311+G(d,p) shows high values of α, β and γ. The B3LYP functional gives the highest first order hyperpolarizability value for (Z)-2-(2-(4-(dimethylamino)benzylidene)-1,1dioxidobenzo[b]thiophen-3(2H)-ylidene)malononitrile (3a) is 373.31 × 10 −30 e.s.u and 486.32 × 10 −30 e.s.u in ethylacetate and dimethylformamide respectively. Effect of bond length alteration (BLA) and bond order alteration (BOA) on first order hyperpolarizability was evaluated. Intrinsic hyperpolarizability shows the compound (Z)-2-(4-(dimethylamino)benzylidene)benzo[b]thiophen-3(2H)-one 1,1-dioxide (1a) intrinsically good. Perturbation potential is found to decrease as absorption energy deceases and hyperpolarizability increases.

Exploring charge transfer effects on linear, non‐linear optical, and dye‐sensitized solar cell properties: A DFT and TD‐DFT investigation of carbazole and aniline‐based dyes

“…The varied percentage of HF exchange is given in Figure S3. We have used three hybrid functional, B3LYP, BHandHLYP [65,66], and PBE1PBE [67,68], two Minnesota functionals M06-HF [69,70] and M06-L [71], one range-separated hybrid functional, CAM-B3LYP [72], and three long-range corrected hybrid functionals, ωB97, ωB97X, and ωB97XD [73][74][75]. And the same set of functionals is also utilized for calculating the NLO characteristics of the chosen sensitizers, coupled with the 6-311++G (d, p) basis set.…”

Charge Transfer as Bridging Correlator for DSSC Efficiency and NLO Property

“…Range-separated hybrid (RSH) functionals provide better results in single point energy computations like computations of vertical excitation (TD-DFT) and NLO properties using coupled perturbed Hartree-Fock (CPHF); hence we have selected RSH functionals, CAM-B3LYP, ωB97, ωB97X and ωB97XD. Becke-half-and-half-Lee-Yang-Parr hybrid functional (BHandHLYP), [63,64] which contains a considerably large amount of HF, was also used. HF/6-311 + + G (d, p) level computations were performed for electron correlation calculations.…”

“…[24] The optimized structures of all the sensitizers did not show any imaginary frequencies confirming that all sensitizers are at a global minimum. TD-DFT computations were carried out using six differ- ChemistrySelect ent functionals, B3LYP, [61,62] BHandHLYP, [63,64] CAM-B3LYP, [57] ωB97, ωB97X, and ωB97XD. [65][66][67] Single-point energy computations, as implemented in Gaussian 09 were used to compute NLO properties using the same functionals and basis set.…”