Plumbing Potentials for Molecules with Up To Tens of Atoms: How to Find Saddle Points and Fix Leaky Holes
Plumbing Potentials for Molecules with Up To Tens of Atoms: How to Find Saddle Points and Fix Leaky Holes
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具有多达数十个原子的分子的管道潜力：如何找到鞍点并修复漏孔
DOI：
10.1021/acs.jpclett.0c01435
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Poirier, Bill
中科院分区：
文献类型：
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作者：
Pandey, Ankit;Poirier, Bill
势能面（PES）在分子动力学中起着不可或缺的作用，但众所周知，在高维空间中很难适当地充实。特别地，未检测到PES孔的存在，即，非物理的鞍点，超过该鞍点，势能任意下降，可以对经典和量子动力学计算产生破坏性影响。在这项研究中，theCrystalalalalalgorithm开发作为一种工具，有效和准确地找到PES孔，以及合法的鞍点，即使在非常大的维配置空间。该方法被应用到三个大规模的PES为当前感兴趣的分子系统：尿嘧啶，萘，甲酸二聚体。低洼PES孔被发现，并位于前两个系统，包括萘，其中没有洞被怀疑，以我们所知。同样，双井，双质子转移异构化鞍点甲酸二聚体也被定位。
Potential energy surfaces (PESs) play an indispensable role in molecular dynamics but are notoriously difficult to flesh out properly in large-dimensional spaces. In particular, the undetected presence of PES holes, i.e., unphysical saddle points beyond which the potential energy drops arbitrarily, can have devastating effects on both classical and quantum dynamics calculations. In this study, theCrystalalgorithm is developed as a tool for efficiently and accurately finding PES holes, as well as legitimate saddle points, even in very large-dimensional configuration spaces. The approach is applied to three large-dimensional PESs for molecular systems of current interest: uracil, naphthalene, and formic acid dimer. Low-lying PES holes are discovered and located for the first two systems—including naphthalene, for which no holes were previously suspected, to the best of our knowledge. Likewise, the double-well, double-proton-transfer isomerization saddle point for formic acid dimer is also located.