Barca Giuseppe M J, Gilbert Andrew T B, Gill Peter M W
Research School of Chemistry , Australian National University , Acton ACT 2601 , Australia.
J Chem Theory Comput. 2018 Mar 13;14(3):1501-1509. doi: 10.1021/acs.jctc.7b00994. Epub 2018 Mar 5.
We present a single-determinant approach to three challenging topics in the chemistry of excited states: double excitations, charge-transfer states, and conical intersections. The results are obtained by using the Initial Maximum Overlap Method (IMOM) which is a modified version of the Maximum Overlap Method (MOM). The new algorithm converges better than the original, especially for these difficult problems. By considering several case studies, we show that a single-determinant framework provides a simple and accurate alternative for modeling excited states in cases where other low-cost methods, such as CIS and TD-DFT, either perform poorly or fail completely.
我们提出了一种单行列式方法，用于处理激发态化学中的三个具有挑战性的主题：双激发、电荷转移态和锥形交叉点。结果是通过使用初始最大重叠方法（IMOM）获得的，该方法是最大重叠方法（MOM）的改进版本。新算法比原始算法收敛性更好，特别是对于这些难题。通过考虑几个案例研究，我们表明，在其他低成本方法（如CIS和TD-DFT）表现不佳或完全失败的情况下，单行列式框架为激发态建模提供了一种简单而准确的替代方法。
