Surface hopping is a very active research area in the recent decades of years. In this work, we derive all necessary equations for a surface hopping method based on Pariser-Parr-Pople (PPP) Hamiltonian and configuration interaction singles (CIS). The surface hopping method is then used to study the dynamics of a cis-polyacetylene chain after it is photoexcited to a high-lying excited state. We find that an excited state may be falsely populated because it is impossible to detect the trivial crossings between noninteracting excited states at time zero using the traditional Min-Cost method.This problem can be solved by screening the initial lattice geometries that do not match a certain condition. By comparison, we discuss the contribution of molecular orbital response with respect to atom displacements (Z matrix) to the nonadiabatic coupling terms and forces, and find that the contribution of Z matrix can be neglected, to some degree. This can greatly save the computational cost.

表面跳跃是近几十年来非常活跃的研究领域。在这项工作中，我们推导出了基于 Pariser-Parr-Pople (PPP) 哈密顿量和配置相互作用单项 (CIS) 的表面跳跃方法的所有必要方程。然后使用表面跳跃方法研究顺式聚乙炔链在光激发到高激发态后的动力学。我们发现激发态可能被错误填充，因为使用传统的 Min-Cost 方法无法检测零时刻非相互作用激发态之间的微不足道的交叉。这个问题可以通过筛选不匹配的初始晶格几何结构来解决。一定的条件。通过比较，我们讨论了分子轨道响应对原子位移的贡献（Z矩阵) 到非绝热耦合项和力，并发现Z矩阵的贡献在某种程度上可以忽略。这样可以大大节省计算成本。