论文标题
自然轨道功能理论中自旋多重组的分析梯度
Analytic gradients for spin multiplets in natural orbital functional theory
论文作者
论文摘要
在天然轨道功能理论中，针对非单词化合物得出了有关核运动的分析能梯度。我们利用多重组的公式来获得一个简单的公式，适用于其地面混合状态的任何多电子系统，总旋转s和所有可能的自旋投影SZ值。我们证明可以在不诉诸线性响应理论或涉及迭代程序的情况下获得分析梯度。它需要进行单个评估，因此可以按计算直通计算积分衍生物，从而提高了Schwarz不平等的筛选有效性。显示了具有许多自旋多重的中小型分子的结果。我们的结果与实验数据和准确的理论平衡几何形状进行了比较。
Analytic energy gradients with respect to nuclear motion are derived for non-singlet compounds in the natural orbital functional theory. We exploit the formulation for multiplets in order to obtain a simple formula valid for any many-electron system in its ground mixed state with a total spin S and all possible spin projection Sz values. We demonstrate that the analytic gradients can be obtained without resorting to linear response theory or involving iterative procedures. It is required a single evaluation, so integral derivatives can be computed on-the-fly along the calculation and thus improve the effectiveness of screening by the Schwarz inequality. Results for small and medium size molecules with many spin multiplicities are shown. Our results are compared with experimental data and accurate theoretical equilibrium geometries.
