Corresponding Active Orbital Spaces along Chemical Reaction Paths

Abstract

The accuracy of reaction energy profiles calculated with multi-configurational electronic structure methods and corrected by multi-reference perturbation theory depends crucially on consistent active orbital spaces selected along the reaction path. However, it has been challenging in all but the simplest cases to choose molecular orbitals that can be considered corresponding in different molecular structures. Here, we demonstrate how active orbital spaces can be selected consistently along reaction coordinates in a fully automatized way. The approach requires no structure interpolation between reactants and products. Instead, it emerges from a synergy of an orbital mapping ansatz [J. Chem. Phys. 2019, 150, 214106] combined with our fully automated active space selection algorithm [J. Chem. Theory Comput. 2016, 12, 1760]. The former we extend by including also virtual orbitals rather than occupied ones only. We demonstrate our algorithm for the potential energy profile of the homolytic carbon-carbon bond dissociation and rotation around the double bond of 1-pentene in the electronic ground state. However, our algorithm also applies to electronically excited Born-Oppenheimer surfaces in a straightforward manner.Comment: 16 pages, 4 figure