Block-Localized Excitation for Excimer Complex and Diabatic Coupling.

ABSTRACT: We describe a block-localized excitation (BLE) method to carry out constrained optimization of block-localized orbitals for constructing valence bond-like, diabatic excited configurations using multistate density functional theory (MSDFT). The method is an extension of the previous block-localized wave function method through a fragment-based ΔSCF approach to optimize excited determinants within a molecular complex. In BLE, both the number of electrons and the electronic spin of different fragments in a whole system can be constrained, whereas electrostatic, exchange, and polarization interactions among different blocks can be fully taken into account of. To avoid optimization collapse to unwanted states, a ΔSCF projection scheme and a maximum overlap of wave function approach have been pr

SUBMITTER: Bao P 

PROVIDER: S-EPMC8214332 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature