Predicting Excited-State Absorption Spectra from Non-Aufbau Configurations.

ABSTRACT: Accurately predicting excited-state absorption (ESA) spectra is crucial for interpreting transient absorption spectroscopy (TAS) features, but it remains a challenge for electronic structure theory. Various density- and wave function-based methods can be used to predict ESA spectra, yet they often struggle to simultaneously achieve accuracy, computational efficiency, and molecular-orbital-based chemical intuition. This work presents a balanced approach for predicting ESA spectra (LR-TDA/ΔSCF) by combining the maximum overlap method (MOM) and Δ self-consistent-field (ΔSCF) with the linear-response Tamm-Dancoff approximation (LR-TDA). LR-TDA/ΔSCF captures excited-state orbital relaxation while preserving the computational efficiency and interpretability of standard LR-TDA calculations. Apply

SUBMITTER: Knepp ZJ 

PROVIDER: S-EPMC12529906 | biostudies-literature | 2025 Oct

REPOSITORIES: biostudies-literature