Accurate calculation of optically induced birefringences in chiral systems using efficient polarized basis sets

Abstract

Using state-of-the-art ab initio methodology, we evaluate universal molecular parameters entering the expressions for various optically induced birefringences in chiral fluids. For this, we use the single and double excitation coupled cluster (CCSD) theory together with Dunning's augmented correlation consistent polarized basis sets of increasing size. As this is the first time these parameters are evaluated for chiral molecules using the CCSD approach, we choose possibly small test systems: a model asymmetric methane molecule, and (R)-fluoro-oxirane. With this choice, the convergence of the molecular parameters with the increase of the basis set size is investigated in detail. The results are compared to those obtained with the LPol-n (n = ds, dl, fs) and the ORP basis sets, and to the corresponding Density Functional Theory (DFT) counterparts. We can conclude that the DFT medium constant values are considerably far from coupled cluster, and therefore, aware of the known excellent performance of the CCSD method in the evaluation of various dynamic responses, we do not recommend the former methodology for accurate evaluation of the present properties. Regarding basis set convergence, the performace of the LPol-ds basis set is more efficient than that of the d-aug-cc-pVDZ set, and therefore, the former basis set can be a good choice when dealing with the study of larger systems.