论文标题
插入式势能表面在非冗余，旋转和翻译不变的坐标中使用插入式势能表面计算
Instanton rate constant calculations using interpolated potential energy surfaces in non-redundant, rotationally and translationally invariant coordinates
论文作者
论文摘要
在插值化学势能表面（PES）中使用人工神经网络的琐碎缺陷，其描述符是笛卡尔坐标的是它们对所考虑的分子的简单翻译和旋转的依赖。可以选择一组不同的描述符来避免此问题，核对间距离，核对间距离或Z-Matrix坐标为三个这样的描述符。目的是在intsanton速率恒定计算中使用插值PES，因此需要在隧道路径附近的坐标上提供有关能量，梯度和黑森的信息。 Instanton理论依赖于平滑合身的Hessians，因此我们在培训程序中使用能量，渐变和黑森人。在从内部坐标到笛卡尔坐标的输出梯度和Hessian的适当反向转变中提出了一个重大挑战。我们对方法，先前的方法和对甲醇氢和异氰酸氢添加氢的氢化速率的恒定计算进行比较。
A trivial flaw in the utilization of artificial neural networks in interpolating chemical potential energy surfaces (PES) whose descriptors are Cartesian coordinates is their dependence on simple translations and rotations of the molecule under consideration. A different set of descriptors can be chosen to circumvent this problem, internuclear distances, inverse internuclear distances or z-matrix coordinates are three such descriptors. The objective is to use an interpolated PES in instanton rate constant calculations, hence information on the energy, gradient and Hessian is required at coordinates in the vicinity of the tunneling path. Instanton theory relies on smoothly fitted Hessians, therefore we use energy, gradients and Hessians in the training procedure. A major challenge is presented in the proper back-transformation of the output gradients and Hessians from internal coordinates to Cartesian coordinates. We perform comparisons between our method, a previous approach and on-the-fly rate constant calcuations on the hydrogen abstraction from methanol and on the hydrogen addition to isocyanic acid.
