Construction of Quasi-diabatic Hamiltonians That Accurately Represent ab Initio Determined Adiabatic Electronic States Coupled by Conical Intersections for Systems on the Order of 15 Atoms. Application to Cyclopentoxide Photoelectron Detachment in the Ful
Construction of Quasi-diabatic Hamiltonians That Accurately Represent ab Initio Determined Adiabatic Electronic States Coupled by Conical Intersections for Systems on the Order of 15 Atoms. Application to Cyclopentoxide Photoelectron Detachment in the Ful
复制标题
准绝热哈密顿量的构造，准确地表示 15 个原子量级系统的从头开始确定的由圆锥交点耦合的绝热电子态。
DOI：
10.1021/acs.jpca.0c02763
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Yarkony, David R.
中科院分区：
文献类型：
--
作者：
Shen, Yifan;Yarkony, David R.
我们提出，系统的中等尺寸，一个合适的框架来构建准绝热哈密顿量，准确地representab initioadiabatic电子结构数据，包括圆锥形交叉的影响。这里介绍的框架之间的差异最小化的拟合预测和theab initiodata在绝热表示，这是奇异的锥形交叉缝。我们定义了一个通用的和灵活的价值函数，允许任意的表示，并提出了一个表示来衡量拟合从头计算的差异，在电子简并附近的几何形状。拟合哈密尔顿算子在采样不足的区域中可能表现不佳，在这种情况下，拟合表示的机器学习理论分析建议正则化以解决缺陷。我们的拟合框架，包括正则化是用来构建完整的39维耦合非绝热势能面环戊氧基相关的环戊氧化物光电子脱离。
We present, for systems of moderate dimension, a fitting framework to construct quasi-diabatic Hamiltonians that accurately representab initioadiabatic electronic structure data including the effects of conical intersections. The framework introduced here minimizes the difference between the fit prediction and theab initiodata obtained in the adiabatic representation, which is singular at a conical intersection seam. We define a general and flexible merit function to allow arbitrary representations and propose a representation to measure the fit–ab initiodifference at geometries near electronic degeneracies. A fit Hamiltonian may behave poorly in insufficiently sampled regions, in which case a machine learning theory analysis of the fit representation suggests a regularization to address the deficiency. Our fitting framework including the regularization is used to construct the full 39-dimensional coupled diabatic potential energy surfaces for cyclopentoxy relevant to cyclopentoxide photoelectron detachment.