Shanghai Frontiers Science Center of Artificial Intelligence and Deep Learning, NYU Shanghai, 567 West Yangsi Road, Shanghai 200126, China.
NYU Shanghai, 567 West Yangsi Road, Shanghai 200126, China.
J Chem Phys. 2023 May 28;158(20). doi: 10.1063/5.0142590.
We present efficient analytical gradients of property-based diabatic states and couplings using a Lagrangian formalism. Unlike previous formulations, the method achieves a computational scaling that is independent of the number of adiabatic states used to construct the diabats. The approach is generalizable to other property-based diabatization schemes and electronic structure methods as long as analytical energy gradients are available and integral derivatives with the property operator can be formed. We also introduce a scheme to phase and reorder diabats to ensure their continuity between molecular configurations. We demonstrate this for the specific case of Boys diabatic states obtained from state-averaged complete active space self-consistent field electronic structure calculations with GPU acceleration in the TeraChem package. The method is used to test the Condon approximation for the hole transfer in an explicitly solvated model DNA oligomer.
我们提出了一种基于拉格朗日形式的有效分析梯度的属性非绝热态和耦合，使用。与以前的公式不同，该方法实现了一种与用于构造非绝热态的绝热态数量无关的计算规模。只要可以获得基于属性的非绝热态和可以形成与属性算子的积分导数的分析能量梯度，该方法就可以推广到其他基于属性的非绝热态方案和电子结构方法。我们还引入了一种方案来对非绝热态进行相位和重新排序，以确保它们在分子构型之间的连续性。我们在 TeraChem 包中使用 GPU 加速的状态平均完全活性空间自洽场电子结构计算获得的 Boys 非绝热态的具体情况下演示了这一点。该方法用于测试在明确定义的溶剂化模型 DNA 寡聚物中孔转移的康登近似。
