Block-diagonalization as a tool for the robust diabatization of high-dimensional potential energy surfaces.
Block-diagonalization as a tool for the robust diabatization of high-dimensional potential energy surfaces.
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DOI：
10.1063/1.4943869
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发表时间：
2016-03
期刊：
影响因子：
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通讯作者：
Florian Venghaus;W. Eisfeld
中科院分区：
文献类型：
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作者：
Florian Venghaus;W. Eisfeld
高维耦合势能面(PESS)的发展是多态量子动力学模拟的关键。在目前的研究中，我们证明，除了实际的脱氢技术外，潜在的电子结构计算中的常见问题可能是脱氢失败的原因。在简要回顾了非对角化的理论背景之后，我们提出了一种基于块对角化的电子结构数据分析方法。该分析工具可以以三种不同的方式使用：第一，它允许检测从头算参考数据的问题，并用于优化电子结构计算的设置。其次，通过识别最重要的耦合，利用块对角化的数据来开发最优的参数化非绝热模型矩阵。第三，利用块对角化数据对非绝热模型的参数进行拟合，为标准或更先进的基于能量的非绝热方法所需的非线性拟合提供了最优的初始猜测。新的方法被证明是通过9个丙叉基的电子态的离解，得到完全耦合的闭合形式的全维(12D)PESS。
Robust diabatization techniques are key for the development of high-dimensional coupled potential energy surfaces (PESs) to be used in multi-state quantum dynamics simulations. In the present study we demonstrate that, besides the actual diabatization technique, common problems with the underlying electronic structure calculations can be the reason why a diabatization fails. After giving a short review of the theoretical background of diabatization, we propose a method based on the block-diagonalization to analyse the electronic structure data. This analysis tool can be used in three different ways: First, it allows to detect issues with the ab initio reference data and is used to optimize the setup of the electronic structure calculations. Second, the data from the block-diagonalization are utilized for the development of optimal parametrized diabatic model matrices by identifying the most significant couplings. Third, the block-diagonalization data are used to fit the parameters of the diabatic model, which yields an optimal initial guess for the non-linear fitting required by standard or more advanced energy based diabatization methods. The new approach is demonstrated by the diabatization of 9 electronic states of the propargyl radical, yielding fully coupled full-dimensional (12D) PESs in closed form.