PNNL

Abstract

Static hyperpolarizabilities of five benchmark systems (hydrogen fluoride, water, acetonitrile, chloroform and para-nitroaniline) are calculated with large basis sets using coupled-cluster response theory and compared to five common DFT methods. These results reveal which methods and basis sets are appropriate for nonlinear optical studies for different types of molecules and provide a means for estimating errors from the quantum chemical approximation when including vibrational contributions or solvent effects at the QM/MM level. The largest calculation reported, which was for 72 electrons in 812 functions at C2v symmetry, took only a few hours on 256 nodes demonstrating that even larger calculations are quite feasible using modern supercomputers.