Calculation of Chemical Reaction Barrier Heights by Multiconfiguration Pair-Density Functional Theory with Correlated Participating Orbitals.

Abstract

The accurate description of reaction barrier heights is challenging for quantum mechanical methods due to the need for a balanced treatment of dynamic and static correlation energies because their importance varies during the course of a chemical reaction. While some regions of potential energy surfaces are well-described by a single-reference wave function or by Kohn-Sham density functional theory, in other cases a multireference treatment is needed. For systems with many active electrons, most accurate multireference methods have prohibitive computational scalings with system size. Multiconfiguration pair-density functional theory, MC-PDFT, is a more affordable multireference approach that computes the total electron correlation energy in a single step by using the multiconfiguration kinetic energy, density, and on-top pair density and an on-top density functional. In this work, we apply MC-PDFT to a benchmark database (DBH24/18) of 24 diverse reaction barrier heights. We explore the role of active space and basis set selection on the performance of MC-PDFT. We find that MC-PDFT is able to calculate reaction barrier heights with a similar accuracy to complete active space second order perturbation theory, CASPT2, but at a lower computational cost, and we find that MC-PDFT is less dependent on basis set selection than CASPT2.