Exploring Systematic Discrepancies in DFT Calculations of Chlorine Nuclear Quadrupole Couplings

摘要: Previous studies have revealed significant discrepancies between density functional theory (DFT)-calculated and experimental nuclear quadrupolar coupling constants (CQ) for chlorine atoms, particularly in ionic solids. Various aspects of the computations are systematically investigated here, including choice DFT functional, basis set convergence, geometry optimization protocol. The effects fast (fs) time-scale dynamics probed using molecular (MD) quantum (NQEs) considered path-integral MD calculations. It is shown that most important factor related to improving accuracy calculations, functionals beyond generalized gradient approximation (GGA) level, such as hybrid meta-GGA functionals, required good correlations with experiment. influence NQEs less than studied systems. A method which invol...