A Flexible, Automated, and Basis-Set-Insensitive Domain-Based Charge-Transfer Decomposition for Correlated Wave Functions and Its Application to Inter- and Intramolecular Cases

We present a flexible, automated, and basis-set-insensitive domain-based charge-transfer (CT) decomposition framework that can be combined with any configuration interaction (CI)-type excited-state wave function. Our approach is not based on excited-state densities and allows the excited-state character to be dissected into local and domain-based CT excitations and measures the individual contributions to each excited state. To guarantee a broad applicability, we introduce two domain-accumulation strategies to translate hole-particle substitutions to domain-domain excitations: a strict domain partitioning and a weighted approach suitable for small molecules and a large number of domains. The performance of both schemes is assessed for inter- and intramolecular CT excitations and various basis sets using EOM-CCSD and its simplified counterpart EOM-pCCD+S. Most importantly, the CT character is, to a large extent, basis-set independent, and both domain-accumulation schemes give consistent results. Overall, our framework provides a robust CT analysis and a domain resolution of the excitation character for a variety of computational setups and excited-state models.