Effects of Empirical Dispersion Energy on the Geometrical Parameters and Relative Energy of a Salicylideneaniline Molecular Switch in the Solid State

The geometries of the enol (E) and keto (K) forms of a crystalline salicylideneaniline molecular switch, (E)-2-methoxy-6-(pyridine-3-yliminomethyl)phenol (PYV3), have been determined using periodic density functional theory (DFT) calculations with a variety of exchange-correlation functionals (XCFs). They are compared to X-ray diffraction (XRD) data as well as to geometries obtained using empirical dispersion energy in the form of the second iteration of Grimme’s scheme, either with its original parameters (DFT-D2) or with parameters revised for the solid state (DFT-D*). Using DFT, a good agreement with experiment on the unit cell parameters is obtained with the PBEsol, PBEsol0, and ωB97X XCFs. DFT-D2 contracts the unit cell too much with all considered XCFs, whereas DFT-D* lessens this effect thus allowing B3LYP, PBE, and PBE0 to achieve reasonable agreement with respect to XRD data. When considering molecular geometries, both DFT and DFT-D* have a similar effect on the bond lengths, both systematically underestimating (overestimating) the length of the single (double) bonds (within 0.003 Å), as well as on valence angles attaining differences of 2 ^◦ with respect to XRD data. The errors on the torsion angles are less spread out with DFT-D* (averaging 1 ^◦) than DFT for which only PBEsol, PBEsol0, and ωB97X perform well. Finally, the relative keto–enol energies, ∆E _KE, have been calculated, showing that the inclusion of dispersion energy stabilizes the keto form more than it does the enol form. This results in the PBE and PBEsol XCFs wrongly predicting the keto form as the most stable form.