This article describes the finite-field (FF) approach for calculating static (hyper)polarizabilities based on the divide-and-conquer (DC) method. The method is assessed by the Hartree-Fock (HF) and post-HF calculations of π-conjugated model systems: a terminal donor or acceptor substituent on polyene chains. The DC-FF approach enables the evaluation of molecular polarizabilities with highly accurate coupled-cluster theory. Numerical assessments demonstrate that the (hyper)polarizabilities calculated by the present DC-FF method agree with the conventional FF results to within a few percent by employing an appropriate buffer size.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry