A Ranked-Orbital Approach to Select Active Spaces for High-Throughput Multireference Computation

The past decade has seen a great increase in the application of high-throughput computation to a variety of important problems in chemistry. However, one area which has been resistant to the high-throughput approach is multireference wave function methods, in large part due to the technicalities of setting up these calculations and in particular the not always intuitive challenge of active space selection. As we look toward a future of applying high-throughput computation to all areas of chemistry, it is important to prepare these methods for large-scale automation. Here, we propose a ranked-orbital approach to select active spaces with the goal of standardizing multireference methods for high-throughput computation. This method allows for the meaningful comparison of different active space selection schemes and orbital localizations, and we demonstrate the utility of this approach across 1120 multireference calculations for the excitation energies of small molecules. Our results reveal that it is helpful to distinguish the method used to generate orbitals from the method of ranking orbitals in terms of importance for the active space. Additionally, we propose our own orbital ranking scheme that estimates the importance of an orbital for the active space through a pair-interaction framework from orbital energies and features of the Hartree-Fock exchange matrix. We call this new scheme the approximate pair coefficient (APC) method and we show that it performs quite well for the test systems presented.

Automated summary

High-throughput computation has been widely applied in the field of chemistry in the past decade, but the active space selection in multireference wave function methods has been a technical challenge. A ranked-orbital approach is proposed to standardize multireference methods for high-throughput computation, allowing for meaningful comparison of different active space selection schemes. A new orbital ranking scheme, the approximate pair coefficient (APC) method, is introduced and shown to perform well in test systems.