کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
501713 863636 2012 7 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Numerical search of discontinuities in self-consistent potential energy surfaces
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی تئوریک و عملی
پیش نمایش صفحه اول مقاله
Numerical search of discontinuities in self-consistent potential energy surfaces
چکیده انگلیسی

Potential energy surfaces calculated with self-consistent mean-field methods are a very powerful tool, since their solutions are, in theory, global minima of the non-constrained subspace. However, this minimization leads to an incertitude concerning the saddle points, that can sometimes be no longer saddle points in larger constrained subspaces (fake saddle points), or can be missing on a trajectory (missing saddle points). These phenomena are the consequences of discontinuities of the self-consistent potential energy surfaces (SPESs). These discontinuities may have important consequences, since they can, for example, hide the real height of an energy barrier, and avoid any use of an SPES for further dynamical calculations, barrier penetrability estimations, or trajectory predictions. Discontinuities are not related to the quality of the production of an SPES, since even a perfectly converged SPES with an ideally fine mesh can be discontinuous. In this paper we explain what the discontinuities are, their consequences, and their origins. We then propose a numerical method to detect and identify discontinuities on a given SPES, and finally we discuss what the best ways are to transform a discontinuous SPES into a continuous one.

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Computer Physics Communications - Volume 183, Issue 10, October 2012, Pages 2035–2041
نویسندگان
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