论文标题
可靠的过渡性能从激发态平均计算
Reliable transition properties from excited-state mean-field calculations
论文作者
论文摘要
Delta-sef-Sensistertent Field Theory（Delta-SCF）是一种概念上简单且计算廉价的方法，用于寻找激发态。使用最大重叠方法指导激发态的优化，Delta-SCF已被证明可以预测具有竞争能力水平的激发能，而精度具有竞争力，有时比TDDFT的激发能更好。在这里，我们基于比以前考虑的更大的分子基准基准-SCF，尤其是，我们研究了三角-SCF在预测过渡偶极矩时的性能，这是光谱强度的基本数量。 Delta-SCF过渡偶极子的潜在衰落是由Delta-SCF地面和激发态的非正交性引起的起源依赖性。我们基于状态的对称正交化提出和测试了对此问题的最简单校正，并证明了其在紫色细菌中从光合天线采样的细菌氯叶叶结构上的使用。
Delta-self-consistent field theory (delta-SCF) is a conceptually simple and computationally inexpensive method for finding excited states. Using the maximum overlap method to guide optimization of the excited state, delta-SCF has been shown to predict excitation energies with a level of accuracy that is competitive with, and sometimes better than, that of TDDFT. Here we benchmark delta-SCF on a larger set of molecules than has previously been considered, and, in particular, we examine the performance of delta-SCF in predicting transition dipole moments, the essential quantity for spectral intensities. A potential downfall for delta-SCF transition dipoles is origin dependence induced by the nonorthogonality of delta-SCF ground and excited states. We propose and test the simplest correction for this problem, based on symmetric orthogonalization of the states, and demonstrate its use on bacteriochlorophyll structures sampled from the photosynthetic antenna in purple bacteria.
