Perimetric coordinate system in potential energy surfaces, spline interpolations, and the study of triatomic reaction dynamics

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• 作者：Yuri Alexando Aoto (1) (2)
  Fernando R. Ornellas (1)
  
• 关键词：Perimetric coordinates sytem ; Pekeris coordinates ; Potential energy surface ; Splines interpolation ; Reaction dynamics
• 刊名：Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta)
• 出版年：2014
• 出版时间：September 2014
• 年：2014
• 卷：133
• 期：9
• 全文大小：5,699 KB
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• 作者单位：Yuri Alexando Aoto (1) (2)
  Fernando R. Ornellas (1)
  
  1. Departamento de Química Fundamental, Instituto de Química, Universidade de S?o Paulo, Av. Prof. Lineu Prestes, 748, S?o Paulo, S?o Paulo, 05508-000, Brazil
  2. Institut für Theoretische Chemie, Universit?t Stuttgart, Pfaffenwaldring 55, 70569, Stuttgart, Germany
  
• ISSN：1432-2234

文摘

Two applications of the perimetric coordinates to triatomic potential energy surfaces are explored. The first is the depiction of level surfaces, providing a global visualization of the potential energy surface. In this representation, the relation among the stationary points and the dissociation channels are easily seen. These level surfaces are shown to be the natural generalization of the well-known two-dimensional level curves of restricted potential energy surfaces; they also allow us to understand the relation of the two-dimensional graphs with the global potential energy surface. Case studies for [Cl, H2], [H, O, Cl] and [O3] potential energy surfaces are discussed in detail. The second application of the perimetric coordinates is the construction of global potential energy surfaces by means of cubic splines, thus avoiding the restrictions related to the triangular inequality. The procedure is straightforward, and a careful analysis of the influence of the interpolation knots on the quality of the potential energy surface was carried out. The potential energy surfaces constructed by such procedure were able to reproduce known dynamical features of the following chemical reactions: Cl?+?H2?→?H?+?HCl, F?+?HD?→?HF(DH)?+?D(H) and O(1D)?+?HCl?→?Cl?+?OH (H?+?OCl).