论文标题
多原子分子的置换式，再现基于内核的势能表面：从甲醛到丙酮
Permutationally Invariant, Reproducing Kernel-Based Potential Energy Surfaces for Polyatomic Molecules: From Formaldehyde to Acetone
论文作者
论文摘要
为多原子分子构建准确的高维分子势能表面（PESS）是具有挑战性的。再现核Hilbert Space（RKHS）插值是一种构造此类PESS的有效方法。但是，当在常规网格上提供输入能时，该方案最有效。因此，即使对于使用高级电子结构计算时，即使对于五角形原子系统来说，所需的参考能量也可能变得非常大。在这里提出了一种有效而健壮的方案来克服这些局限性，并应用于为具有多达10个原子的系统构建高维pess。使用能量以及梯度减少所需的输入数据数量，从而使系数的数量保持在可管理的大小。对于高度对称的CH $ _4 $分子，测试并明确证明了在内核产品中正确实现置换对称性。
Constructing accurate, high dimensional molecular potential energy surfaces (PESs) for polyatomic molecules is challenging. Reproducing Kernel Hilbert space (RKHS) interpolation is an efficient way to construct such PESs. However, the scheme is most effective when the input energies are available on a regular grid. Thus the number of reference energies required can become very large even for penta-atomic systems making such an approach computationally prohibitive when using high-level electronic structure calculations. Here an efficient and robust scheme is presented to overcome these limitations and is applied to constructing high dimensional PESs for systems with up to 10 atoms. Using energies as well as gradients reduces the number of input data required and thus keeps the number of coefficients at a manageable size. Correct implementation of permutational symmetry in the kernel products is tested and explicitly demonstrated for the highly symmetric CH$_4$ molecule.
