American Chemical Society
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Extending the ASS1ST Active Space Selection Scheme to Large Molecules and Excited States

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journal contribution
posted on 2020-07-20, 17:14 authored by Abhishek Khedkar, Michael Roemelt
Multireference electronic structure methods based on the CAS (complete active space) ansatz are well-established as a means to provide reliable predictions of physical properties of strongly correlated systems. A critical aspect of every CAS calculation is the selection of an adequate active space, in particular as the boundaries for tractable active spaces have been shifted significantly with the emergence of efficient approximations to the Full-CI problem like the density matrix renormalization group and full-CI quantum Monte Carlo. Recently, we proposed an active space selection based on first-order perturbation theory (ASS1ST) that yields satisfactory results for the electronic ground state of a variety of strongly correlated systems. In this work, we present a state-averaged extension of ASS1ST (SA-ASS1ST) that determines suitable active spaces when electronically excited states are targeted. Furthermore, the computational costs of the single state and state-averaged variants are significantly reduced by a simple approximation that avoids the most expensive step of the original method, the evaluation of active space four-electron reduced density matrices, altogether. After the applicability of the approximation is established, test calculations on a biomimetic Mn4O4 cluster demonstrate the enhanced range of ASS1ST in terms of system size and complexity. Furthermore, calculations on [VOCl4]2, MeMn­(CO)3-α-diimine, and anthracene show that SA-ASS1ST suggests well-suited active spaces to describe d → d and charge-transfer excitations in transition-metal complexes as well as π → π* excitations in aryl compounds. Finally, the application of ASS1ST on multiple points of the potential energy surface of Cr2 illustrates the applicability of the method even when extremely complicated bonding patterns are met. More importantly, however, it highlights the necessity to use special strategies when different points of a potential energy surface are investigated, e.g., during chemical reactions.