Carlson Rebecca K, Truhlar Donald G, Gagliardi Laura
Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455, United States.
J Chem Theory Comput. 2015 Sep 8;11(9):4077-85. doi: 10.1021/acs.jctc.5b00609. Epub 2015 Aug 6.
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.
我们将多组态对密度泛函理论（MC-PDFT）的顶密度泛函进行扩展，使其包含顶密度的梯度以及密度的梯度。我们发现该理论对这种扩展具有合理的稳定性；此外，它对于含过渡金属的分子提供了更高的精度。我们通过将扩展的顶密度泛函应用于Cr2、Cu2、Ag2、Os2和Re2Cl8(2-) 以及我们之前包含56个关于键解离能、势垒高度、反应能、质子亲和能和水二聚体数据的数据库来说明这些泛函。MC-PDFT的性能与CASPT2相当或更好。
