CAS without SCF—Why to use CASCI and where to get the orbitals

• Published in: The Journal of chemical physics 2021-03, Vol.154 (9), p.090902-090902
• Main Authors: Levine, Benjamin G., Durden, Andrew S., Esch, Michael P., Liang, Fangchun, Shu, Yinan
• Format: Article
• Language: English
• Subjects: Approximation; Complete-active space self-consistent field; Configuration interaction; Electronic structure; Excitation; Excitation energies; Hartree approximation; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Mathematical analysis; Nanomaterials; Orbitals; Physics; Potential energy; Self consistent fields
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0042147

The complete active space self-consistent field (CASSCF) method has seen broad adoption due to its ability to describe the electronic structure of both the ground and excited states of molecules over a broader swath of the potential energy surface than is possible with the simpler Hartree–Fock approximation. However, it also has a reputation for being unwieldy, computationally costly, and un-black-box. Here, we discuss a class of alternatives, complete active space configuration interaction (CASCI) methods, paying particular attention to their application to electronic excited states. The goal of this Perspective is fourfold. First, we argue that CASCI is not merely an approximation to CASSCF, in that it can be designed to have important qualitative advantages over CASSCF. Second, we present several insights drawn from our experience experimenting with different schemes for computing orbitals to be employed in CASCI. Third, we argue that CASCI is well suited for application to nanomaterials. Finally, we reason that, with the rise in new low-scaling approaches for describing multireference systems, there is a greater need than ever to develop new methods for defining orbitals that provide an efficient and accurate description of both static correlation and electronic excitations in a limited active space.