论文标题
通过块局部激发法
Diabatic States,Couplings and Potential Energy Surfaces through the Block Localized Excitation Method
论文作者
论文摘要
我们提出了一种新的块局部激发方法（BLE）方法，以直接构建绝世激发态，而无需首先计算绝热状态。新方法能够将任何电子，旋转和激发保持在任何分子间和分子内系统的块中。同时，可以完全考虑不同块之间的静电，交换和极化相互作用。为此，采用了一种新的Delta-SCF项目方法和最大的波函数重叠方法来获得具有轨道弛豫的局部激发态，并使用类似于多类DFT（MSDFT）方法的方法获得了它们之间的耦合。数值结果表明，新的BLE方法在计算单元激发能量转移（SEET）和三重态能量激发转移（TEET）过程以及激发态分子间势能表面的电子耦合方面是准确的。
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.
