Qu Chen, Yu Qi, Bowman Joel M
Department of Chemistry, Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, USA; email:
Annu Rev Phys Chem. 2018 Apr 20;69:151-175. doi: 10.1146/annurev-physchem-050317-021139. Epub 2018 Jan 31.
Over the past decade, about 50 potential energy surfaces (PESs) for polyatomics with 4-11 atoms and for clusters have been calculated using the permutationally invariant polynomial method. This is a general, mainly linear least-squares method for precise mathematical fitting of tens of thousands of electronic energies for reactive and nonreactive systems. A brief tutorial of the methodology is given, including several recent improvements. Recent applications to the formic acid dimer (the current record holder in size for a reactive system), the H-HO complex, and four protonated water clusters [H(HO)] are given. The last application also illustrates extension to large clusters using the many-body representation.
在过去十年中，使用置换不变多项式方法已经计算了大约50个含有4至11个原子的多原子分子以及团簇的势能面（PES）。这是一种通用的、主要基于线性最小二乘法的方法，用于对反应性和非反应性系统的数万种电子能量进行精确的数学拟合。本文给出了该方法的简要教程，包括一些近期的改进。还介绍了该方法在甲酸二聚体（目前反应性系统中尺寸方面的记录保持者）、H-HO络合物以及四个质子化水团簇[H(HO)]上的近期应用。最后一个应用还展示了如何使用多体表示法扩展到大型团簇。
