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Multiconfiguration Pair-Density Functional Theory: A Fully Translated Gradient Approximation and Its Performance for
Rebecca K Carlson1, Donald G Truhlar1, Laura Gagliardi1
1Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
Abstract:
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 Cr2, Cu2, Ag2, Os2, and Re2Cl8(2-) 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.
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