Efficient and robust approximations to the full configuration interaction (full-CI) method such as the density matrix renormalization group (DMRG) and the full-CI quantum Monte Carlo (FCIQMC) algorithm allow for multiconfigurational self-consistent field (MC-SCF) calculations of molecules with many strongly correlated electrons. This opens up the possibility to treat large and complex systems that were previously untractable, but at the same time it calls for an efficient and reliable active space selection as the choice of how many electrons and orbitals enter the active space is critical for any multireference calculation. In this work we propose an Active Space Selection based on 1st order perturbation theory (ASS1ST) that follows a "bottom-up" strategy and utilizes a set of quasi-natural orbitals together with sensible thresholds for their occupation numbers. The required quasi-natural orbitals are generated by diagonalizing the virtual and internal part of the one-electron reduced density matrix that is obtained from strongly contracted n-electron valence perturbation theory (SC-NEVPT) on top of a minimal active space calculation. Self-consistent results can be obtained when the proposed selection scheme is applied iteratively. Initial applications on four chemically relevant benchmark systems indicate the capabilities of ASS1ST. Eventually, the strengths and limitations are critically discussed.

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.

Transition metal chemistry is a challenging playground for quantum chemical methods owing to the simultaneous presence of static and dynamic electron correlation effects in many systems. Wavefunction based multireference (MR)...

The selective reduction of CO 2 is of high interest toward future applications as a C1-building block. Therefore, metal complexes that allow for the formation of specific CO 2 reduction products under distinct reaction conditions are necessary. A detailed understanding of the CO 2 reduction pathways on a molecular level is, however, required to help in designing catalytic platforms for efficient CO 2 conversion with specific product formation. Reported herein is a unique example of a solvent-controlled reduction of CO 2 using a Triphos-based iron hydride complex. In THF, CO 2 reduction selectively leads to CO formation, whereas experiments in acetonitrile exclusively afford formate, HCOO − . In order to explain the experimental findings, theoretical calculations of the reaction pathways were performed and further demonstrate the importance of the applied solvent for a selective reduction of CO 2 .