Diabatic States,Couplings and Potential Energy Surfaces through the Block Localized Excitation Method

Abstract: We propose a new block localized excitation (BLE) method to directly construct diabatic excited states without the need to first compute the adiabatic states. The new method is capable to keep any electrons, spins, and excitations localized in any divided blocks of intermolecular and intramolecular systems. At the same time, the electrostatic, exchange, and polarization interactions between different blocks can be fully taken account of. To achieve this, a new delta-SCF project method and the maximum wavefunction overlap method are employed to obtain localized excited states with orbitals relaxation, and the coupling between them are obtained using approaches similar to the multistate DFT (MSDFT) method. Numerical results show that the new BLE method is accurate in calculating the electronic couplings of the singlet excitation energy transfer (SEET) and triplet energy excitation transfer (TEET) processes, as well as the excited-state intermolecular potential energy surface.