Nonorthogonal Configuration Interaction of Constraint-Based Orbital-Optimized Excited States: A Versatile Method for Theoretical Photochemistry.

ABSTRACT: We introduce a nonorthogonal configuration interaction (NOCI) scheme for COOX, our recently developed constraint-based orbital-optimized excited state method [Kussmann et al. J. Chem. Theory. Comput., 2024, 20, 8461], which enables a targeted variational optimization of electronically excited states through constrained density functional theory. COOX is shown to be a more reliable source of NOCI reference configurations compared to orbital-optimized methods based on the ΔSCF scheme. The versatility and stability of NOCI-COOX are illustrated for the 2 ¹A_g state of all-E-polyenes, conical intersections, core excitations, and other cases that are challenging to traditional linear-response time-dependent DFT approaches, and exemplary calculatio

SUBMITTER: Lemke Y 

PROVIDER: S-EPMC12573764 | biostudies-literature | 2025 Oct

REPOSITORIES: biostudies-literature