论文标题
基于密度功能的紧密结合方法的地面到刺激的衍生耦合：半本地和远程校正配方
Ground-to-excited derivative couplings for the density functional based tight-binding method: Semi-local and long-range corrected formulations
论文作者
论文摘要
提出了在地面和激发态之间基于密度功能的紧密结合方法（DFTB）的非绝热耦合向量的推导。分析结果对于半本地和远程校正的DFTB都是有效的，包括所有必需的pulay项。电子翻译因子导致对预先计算积分的Slater-Koster方案的概念简化。与从数值衍生物获得的标量耦合相比，本方法在计算上更有效，可以应用于具有数百个原子的系统。 DFTB衍生耦合的准确性通过使用半局部和混合交换相关功能的全密度功能理论（DFT）计算来评估，并具有令人鼓舞的结果。如Furan的案例研究所举例说明，DFTB提供了非绝热耦合向量，这些耦合向量在圆锥交叉口附近的大小和方向上接近DFT对应物。
A derivation of non-adiabatic coupling vectors for the density functional based tight binding method (DFTB) between ground and excited states is presented. The analytical result is valid both for semi-local and long-range corrected DFTB and includes all required Pulay terms. Electron-translation factors lead to a conceptual simplification of the Slater-Koster scheme for precomputed integrals. Compared to scalar couplings obtained from numerical derivatives, the present approach is computationally more efficient and can be applied to systems with hundreds of atoms. The accuracy of DFTB derivative couplings is assessed by comparison to full density functional theory (DFT) calculations using semi-local and hybrid exchange-correlation functionals with promising results. As exemplified by a case study of furan, DFTB provides non-adiabatic coupling vectors that are close to DFT counterparts in size and direction also in the vicinity of conical intersections.
