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Calculus of variations as a basic tool for modeling of reaction paths and localization of stationary points on potential energy surfaces

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The theory of calculus of variations is a mathematical tool which is widely used in different scientific areas in particular in physics and chemistry. This theory is strongly related with optimisation. In fact the former seeks to optimise an integral related with some physical magnitude over some space to an extremum by varying a function of the coordinates. On the other hand, reaction paths and potential energy surfaces, in particular their stationary points, are the basis of many chemical theories, in particular reactions rate theories. We present a review where it is gathered together the variational nature of many types of reaction paths: steepest descent, Newton trajectories, artificial force induced reaction (AFIR) paths, gradient extremals, and gentlest ascent dynamics (GAD) curves. The variational basis permits to select the best optimisation technique in order to locate important theoretical objects on a potential energy surface.

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BOFILL I VILLÀ, Josep m., QUAPP, Wolfgang. Calculus of variations as a basic tool for modeling of reaction paths and localization of stationary points on potential energy surfaces. _Molecular Physics_. 2019. [consulta: 20 de gener de 2026]. ISSN: 0026-8976. [Disponible a: https://hdl.handle.net/2445/159363]

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