Can we understand the branching of reaction valleys for more than two degrees of freedom?

被引:0
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作者
Wolfgang Quapp
机构
[1] Universität Leipzig,Mathematisches Institut
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关键词
Valley-ridge-inflection point; VRI manifold; Potential energy surface; Newton trajectory;
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摘要
The model of the chemical reaction path is fundamental in Chemistry. We usually understand it as the pathway along a valley of the potential energy surface (PES). However, often a valley bifurcation occurs. This is controlled by a valley-ridge-inflection point (VRI). Up to now, 2-dimensional (2D) figures of a PES govern our understanding. But for more degrees of freedom, this might be misleading. Here, we explain the matter over a 3D configuration space; the PES is then a 3D hypersurface in an R4\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$R^4$$\end{document}. In this case a visualization is possible. We still can project curves on the PES down into the R3\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$R^3$$\end{document} of the configuration space. A method for the calculation of Newton trajectories (NT) is applied, because NTs bifurcate at VRI points. The example used is a simple mathematical test function. It ends with a threefold combination manifold of three 1D VRI lines. The intersection of the VRI lines forms a super-VRI point. The corresponding singular NT at the super-VRI point has eight branches.
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页码:137 / 148
页数:11
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