Automation of Active Space Selection for Multireference Methods via Machine Learning on Chemical Bond Dissociation.

Predicting and understanding the chemical bond is one of the major challenges of computational quantum chemistry. Kohn-Sham density functional theory (KS-DFT) is the most common method, but approximate density functionals may not be able to describe systems where multiple electronic configurations are equally important. Multiconfigurational wave functions, on the other hand, can provide a detailed understanding of the electronic structures and chemical bonds of such systems.

Transition Metal Spin-State Energetics by MC-PDFT with High Local Exchange.

The energetics of the spin states of transition metal complexes have been explored with a variety of electronic structure methods, but the calculations require a compromise between accuracy and affordability. In this work, the spin splittings of several iron complexes are studied with multiconfiguration pair-density functional theory (MC-PDFT). The results are compared to previously published results obtained by complete active space second-order perturbation theory (CASPT2) and CASPT2 with coupled-cluster semicore correlation (CASPT2/CC).

MC-PDFT can calculate singlet-triplet splittings of organic diradicals.

The singlet-triplet splittings of a set of diradical organic molecules are calculated using multiconfiguration pair-density functional theory (MC-PDFT), and the results are compared with those obtained by Kohn-Sham density functional theory (KS-DFT) and complete active space second-order perturbation theory (CASPT2) calculations. We found that MC-PDFT, even with small and systematically defined active spaces, is competitive in accuracy with CASPT2, and it yields results with greater accuracy and precision than Kohn-Sham DFT with the parent functional. MC-PDFT also avoids the challenges associated with spin contamination in KS-DFT.

Systematic design of active spaces for multi-reference calculations of singlet-triplet gaps of organic diradicals, with benchmarks against doubly electron-attached coupled-cluster data.

Singlet-triplet gaps in diradical organic π-systems are of interest in many applications. In this study, we calculate them in a series of molecules, including cyclobutadiene and its derivatives and cyclopentadienyl cation, by using correlated participating orbitals within the complete active space (CAS) and restricted active space (RAS) self-consistent field frameworks, followed by second-order perturbation theory (CASPT2 and RASPT2). These calculations are evaluated by comparison with the results of doubly electron-attached (DEA) equation-of-motion (EOM) coupled-cluster (CC) calculations with up to 4-particle-2-hole (4p-2h) excitations.

Origin of the Strong Interaction between Polar Molecules and Copper(II) Paddle-Wheels in Metal Organic Frameworks.

The copper paddle-wheel is the building unit of many metal organic frameworks. Because of the ability of the copper cations to attract polar molecules, copper paddle-wheels are promising for carbon dioxide adsorption and separation. They have therefore been studied extensively, both experimentally and computationally.