Self-Adapting Short-Range Correlation Functional for Complete Active Space-Based Approximations.

ABSTRACT

We propose a short-range correlation energy correction tailored for active space wave function models. The correction relies on a short-range multideterminant correlation functional computed with a local range-separation parameter that self-adapts to the underlying wave function. This approach is analogous to that of Giner et al. [J. Chem. Phys. 2018, 149, 194301] which addresses the basis set incompleteness error, with the vital distinction that in our protocol the range-separation parameter remains finite in the complete basis set limit, ensuring nonzero short-range correlation. The proposed correlation functional compensates for the missing short-range correlation via two mechanisms (i) an automatically adapting short-range parameter, which gauges the missing correlation in the electron vicinity, and (ii) the functional's explicit dependence on the on-top pair density, which reduces short-range correlation in regions where electron correlation is mainly static. We integrate our method into the multireference adiabatic connection theory for CASSCF wave functions. The performance of the introduced CAS-AC0-(c,md) model is verified by calculating potential energy curves for alkaline-earth metal dimers (Be2, Mg2, Ca2) and for the chromium dimer, in all cases obtaining promising results.