Multiconfiguration Pair-Density Functional Theory: A Fully Translated Gradient Approximation and Its Performance for Transition Metal Dimers and the Spectroscopy of Re2Cl82-

作者：Carlson Rebecca K; Truhlar Donald G^*; Gagliardi Laura

来源：Journal of Chemical Theory and Computation, 2015, 11(9): 4077-4085.

DOI：10.1021/acs.jctc.5b00609

We extend the on-top density functional of multiconfiguration pair-density functional theory (MC-PDFT) to include the gradient of the on-top density as well as the gradient of the density. We find that the theory is reasonably stable to this extension; furthermore, it provides improved accuracy for molecules containing transition metals. We illustrate the extended on-top density functionals by applying them to Cr-2, Cu-2, Ag-2, Os-2, and Re2Cl82- as well as to our previous database of 56 data for bond dissociation energies, barrier heights, reaction energies, proton affinities, and the water dimer. The performance of MC-PDFT is comparable to or better than that of CASPT2.

• 出版日期2015-9