Electronic Excited States from the Adiabatic-Connection Formalism with Complete Active Space Wave Functions.

Abstract

It is demonstrated how the recently proposed multireference adiabatic-connection (AC) approximation for electron correlation energy ( Pernal , K. Electron Correlation from the Adiabatic Connection for Multireference Wave Functions . Phys. Rev. Lett. 2018 , 120 , 013001 ) can be extended to predicting correlation energy in excited states of molecules. It is the first successful application of the AC approach to computing excited-states energies of molecules using a complete active space (CAS) wave function as a reference. The unique feature of the AC-CAS approach with respect to popular methods such as CASPT2 and NEVPT2 is that it requires only one- and two-particle reduced density matrices, making it possible to efficiently treat large spaces of active electrons. Application of the simpler variant of AC, the AC0, which is based on the first-order expansion of the AC integrand at the uncorrelated system limit, to excited states yields excitation energies with accuracy rivaling that of the NEVPT2 method but at greatly reduced computational cost.