Automated Active Space Selection with Dipole Moments

Abstract

Multireference calculations can provide accurate information of systems with strong correlation, which have increasing importance in the development of new molecules and materials. However, selecting a suitable active space for multireference calculations is nontrivial, and the selection of an unsuitable active space can sometimes lead to results that are not physically meaningful. Active space selection often requires significant human input, and the selection that leads to reasonable results often goes beyond chemical intuition. In this work, we have developed and evaluated two protocols for automated selection of the active space for multireference calculations based on a simple physical observable, the dipole moment, for molecules with nonzero ground-state dipole moments. One protocol is based on the ground-state dipole moment, and the other is based on the excited-state dipole moments. To evaluate the protocols, we constructed a dataset of 1275 active spaces from 25 molecules, each with 51 active space sizes considered, and have mapped out the relationship between the active space, dipole moments, and vertical excitation energies. We have demonstrated that, within this dataset, our protocols allow one to choose among a number of accessible active spaces one that is likely to give reasonable vertical excitation energies, especially for the first three excitations, with no parameters manually decided by the user. We show that, with large active spaces removed from consideration, the accuracy is similar and the time-to-solution can be reduced by more than 10 fold. We also show that the protocols can be applied to potential energy surface scans and determining the spin states of transition metal oxides.