Zeroth-order regular approximation approach to molecular parity violation -: art. no. 042105

We present an ab initio (quasirelativistic) two-component approach to the computation of molecular parity-violating effects which is based on the zeroth-order regular approximation (ZORA). As a first application, we compute the parity-violating energy differences between various P and M conformations of C-2-symmetric molecules belonging to the series H2X2 with X=O, S, Se, Te, Po. The results are compared to previously reported (relativistic) four-component Dirac-Hartree-Fock-Coulomb (DHFC) data. Relative deviations between ZORA and DHFC values are well below 2% for diselane and the heavier homologs whereas somewhat larger relative deviations are observed for the lighter homologs. The larger deviations for lighter systems are attributed to the (nonlocal) exchange terms coupling large and small components, which have been neglected in the present ZORA implementation. For heavier systems these play a minor role, which explains the good performance of the ZORA approach. An excellent performance, even for lighter systems, is expected for a related density-functional-theory-based ZORA because then the exchange terms coupling large and small components are absent.