Theoretical study on the photophysical properties of chiral mononuclear and dinuclear zinc complexes

Benchmarking computational methods and influence of guest conformation on chirogenesis in zinc porphyrin complexes

“…All these eight functionals have been successfully applied for TD-DFT simulations 44,45,73,[84][85][86][87][88] including simulations of the CD spectra of metal complexes. [89][90][91][92][93][94][95][96][97][98][99] In addition to the functionals, two basis sets of different sizes: cc-pVDZ [100][101][102] and cc-pVTZ 42,91,[100][101][102] were considered. As reported previously, for UV and CD spectra simulations the double-zeta basis set is considered to be accurate.…”

“…As reported previously, for UV and CD spectra simulations the double-zeta basis set is considered to be accurate. 84,90 However, cc-pVTZ was also tested, since upon using the triple zeta basis set, a better agreement was obtained with the experimental energies for channel rhodopsins 103 and bis(chelate) copper(I) guanidine-quinoline complex. 91 Moreover, it was reported that the basis sets of at least triple zeta quality is needed for calculations of the rotatory strengths.…”

“…Both these continuum models were successfully applied in TD-DFT simulations. 88,90,[112][113][114] Indeed, there are contradictory results on the solvent role on CD spectral simulations. While, in some cases it was stated that the simulated CD spectra were very sensitive to the solvent used, 38,115,116 there are other examples reporting that inclusion of the solvent effects did not improve the agreement with the experimental spectra.…”

“…While, in some cases it was stated that the simulated CD spectra were very sensitive to the solvent used, 38,115,116 there are other examples reporting that inclusion of the solvent effects did not improve the agreement with the experimental spectra. 88,90 The CD spectra were visualized using GaussView 6. 117 For spectral building a bandwidth of 0.1 eV was used as it had the best agreement with the experimental spectra ( Figure S1).…”

“…All these eight functionals were previously successfully used for TD-DFT simulations including CD spectra of metal complexes. 89,90 The test calculations were performed using the cc-pVDZ basis set, since, as shown previously, the double-zeta basis set was accurate enough for UV and CD spectral simulations. 84,90,116 Also, to include the implicit solvent effects, the SMD continuum model was used.…”