Analytic Gradients for the Long-Range-Corrected XYG3 Type of Doubly Hybrid Density Functionals: Theory, Implementation, and Assessment.

An analytic gradient algorithm for the long-range-corrected (lrc-) XYG3 type of doubly hybrid functionals has been derived and implemented. Due to the introduction of a long-range second-order perturbation (lrPT2) as the correction, the Z -vector equations need to be modified, where the construction of a unique total Lagrangian of the method is required. Geometry optimizations using lrc-XYG3 and lrc-XYGJ-OS have then been applied to the A21 data set that consists of 21 noncovalently interacting systems with CCSD(T) reference data for structures, in order to testify the idea of introducing lrPT2 for a better description of intermolecular interactions. While lrc-XYG3 was observed to offer a better description in dispersion-dominant systems as compared to the XYG3 functional, lrc-XYGJ-OS stands out with an overall better balanced performance in reproducing intermolecular geometries.