SCC-DFTB calculation of the static first hyperpolarizability: from gas phase molecules to functionalized surfaces

The performance of the self-consistent charge density functional tight binding (SCC-DFTB) method for calculating the first hyperpolarizability of π-conjugated compounds has been assessed with respect to results obtained with high-level ab initio methods and density functional theory (DFT). The SCC-DFTB method performs similarly or better than DFT with the PBE XC functional. Thus, if for small π-conjugated linkers SCC-DFTB can reproduce trends, for longer chains the first hyperpolarizabilities are overestimated. In the case of push-pull thiophenes, the β values are strongly overestimated, as it is also the case with the B3LYP and PBE XC functionals. On the other hand, the SCC-DFTB method closely reproduces the evolution of β in p-disubstituted benzenes as a function of the donor and acceptor groups, as estimated at the MP2 level. The reliability of SCC-DFTB to determine the bond length alternation and the dihedral angles between the aromatic rings has also been tackled, demonstrating that both are underestimated. Overall, the SCC-DFTB calculations are of the same quality as those performed with the conventional PBE XC functional on which the method was parameterized but the SCC-DFTB calculations are computationally very little demanding, and it can therefore be adopted for very large systems for screening nonlinear optical materials as well as for assessing structure-property relationships. This is illustrated with an application on the first hyperpolarizability of an indolino-oxazolidine molecular switch grafted on a SiO2 surface. This has enabled to pinpoint (i) the effect of the surface on the donor/acceptor character of the linking substituent, (ii) the impact of molecular orientation, (iii) the role of a spacer between the π-conjugated switch and the surface, (iv) the global effect of the surface on the β contrast, and also (v) the fact that the molecular switches can maintain this contrast when adsorbed.