Optimal-Reference Excited State Methods: Static Correlation at Polynomial Cost with Single-Reference Coupled-Cluster Approaches

Abstract

Accurate yet efficient modeling of chemical systems with pronounced static correlation in their excited states remains a significant challenge in quantum chemistry, as most electronic structure methods that can adequately capture static correlation scale factorially with system size. Researchers are often left with no option but to use more affordable methods that may lack the accuracy required to model critical processes in photochemistry such as photolysis, photocatalysis, and non-adiabatic relaxation. A great deal of work has been dedicated to refining single-reference descriptions of static correlation in the ground state via ``addition-by-subtraction'' coupled cluster methods such as pair coupled cluster with double substitutions (pCCD), singlet-paired CCD (CCD0), triplet-paired CCD (CCD1), and CCD with frozen singlet- or triplet-paired amplitudes (CCDf0/CCDf1). By combining wave functions derived from these methods with the intermediate state representation (ISR), we gain insights into the extensibility of single-reference coupled cluster theory's coverage of static correlation to the excited state problem. Our CCDf1-ISR(2) approach is robust in the face of static correlation and provides enough dynamical correlation to accurately predict excitation energies to within about 0.2~eV in small organic molecules. We also highlight distinct advantages of the Hermitian ISR construction, such as the avoidance of pathological failures of equation-of-motion methods for excited state potential energy surface topology. Our results prompt us to continue exploring optimal single-reference theories (excited state approaches that leverage dependence on the initial reference wave function) as a potentially economical approach to the excited state static correlation problem.