Valley ridge inflection points on the potential energy surfaces of H2S, H2Se and H2CO

文献信息

发布日期 2001-06-14
DOI 10.1039/B102053F
影响因子 3.676
作者

Wolfgang Quapp, Vladlen Melnikov


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摘要

The MP2/6-31G** potential energy surfaces (PES) of the hydrogen sulfide molecule and of the formaldehyde molecule, as well as the MP2/3-21G** PES of the hydrogen selenide molecule are used as qualitative models to locate curves of valley ridge inflection (VRI) points. Crossing points between VRI curves, or VRI manifolds, and approximations of the reaction path allow the identification of a symmetric bifurcation of an assumed reaction path. The recently proposed method of following the reduced gradient is used to calculate reaction path approximations together with their possible bifurcations. The VRI points are calculated with the help of Branin's method, the desingularized global Newton method. The results achieved for the three-atom H2S and H2Se are further extended to the four-atom formaldehyde molecule, being a six-dimensional problem, where the directions of symmetrical unimolecular isomerization and dissociation are treated. We discuss the significance of VRI curves.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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