Continuous Localized Orbital Corrections to Density Functional Theory: B3LYP-CLOC

Our previous works have demonstrated the ability of our localized orbital correction (LOC) methodology to greatly improve the accuracy of various thermochemical properties at the stationary points of the density functional theory (DFT) reaction coordinate (RC). Herein, we extend this methodology from stationary points to the entire RC connecting any stationary points by developing continuous localized orbital corrections (CLOCs). We show that the resultant method, DFT-CLOC, is capable of producing RCs with far greater accuracy than uncorrected DFT and yet requires negligible computational cost beyond the uncorrected DFT calculations. Various post-Hartree-Fock (post-HF) reaction coordinate profiles were used, including a sigmatropic shift, Diels-Alder reaction, electrocyclization, carbon radical, and three hydrogen radical reactions to show that this method is robust across multiple reaction types of general interest.