Extended separated-pair approximation for transition metal potential energy curves.

Abstract

Developing a computational method that is both affordable and accurate for transition-metal chemistry is a major challenge. The bond dissociation energies and the potential energy curves are two important targets for theoretical prediction. Here, we investigate the performance of multiconfiguration pair-density functional theory (MC-PDFT) based on wave functions calculated by the complete-active-space (CAS) and generalized active space (GAS) self-consistent-field (SCF) methods for three transition-metal diatomics (TiC, TiSi, and WCl) for which accurate bond energies are available from recent experiments. We compare the results to those obtained by CAS second-order perturbation theory (CASPT2) and Kohn-Sham DFT (KS-DFT). We use six systematic methods to choose the active spaces: (1) we put the bonding orbitals, antibonding orbitals, and singly occupied nonbonding orbitals into the active space in the first method; (2) we also put s and p valence orbitals into the active space; we tried two levels of correlated participating orbitals (CPO) active spaces: (3) nominal CPO (nom-CPO) and (4) extended CPO (ext-CPO); and we used (5) the separated-pair (SP) approximation and (6) a new method presented here called extended separate pairs (ESP) approximation to divide the nom-CPO active space into subspaces. Schemes 1-4 are carried out within the CAS framework, and schemes 5 and 6 are carried out in the GAS framework to eliminate deadwood configurations. For TiC and TiSi, we used all six kinds of active spaces. For WCl, we used three active spaces (nom-CPO, SP, and ESP). We found that MC-PDFT performs better than both CASPT2 and KS-DFT. We also found that the SP (for TiSi) and ESP (for TiC and WCl) approximations are particularly appealing because they make the potential curves smoother and significantly decrease the computational cost of CASSCF calculations. Furthermore, ESP-PDFT can be as accurate as CAS-PDFT.