Rock climbing: A local-global algorithm to compute minimum energy and minimum free energy pathways

• Published in: The Journal of chemical physics Vol. 147; no. 15; pp. 152718 - 152727
• Main Authors: Templeton, Clark, Chen, Szu-Hua, Fathizadeh, Arman, Elber, Ron
• Format: Journal Article
• Language: English
• Published: United States American Institute of Physics 21.10.2017; AIP Publishing LLC
• Subjects: Algorithms; Free energy; Mathematical analysis; Organic chemistry; Physics; Special Topic: Reaction Pathways
• ISSN: 0021-9606; 1089-7690; 1089-7690
• DOI: 10.1063/1.4986298

The calculation of minimum energy or minimum free energy paths is an important step in the quantitative and qualitative studies of chemical and physical processes. The computations of these coordinates present a significant challenge and have attracted considerable theoretical and computational interest. Here we present a new local-global approach to study reaction coordinates, based on a gradual optimization of an action. Like other global algorithms, it provides a path between known reactants and products, but it uses a local algorithm to extend the current path in small steps. The local-global approach does not require an initial guess to the path, a major challenge for global pathway finders. Finally, it provides an exact answer (the steepest descent path) at the end of the calculations. Numerical examples are provided for the Mueller potential and for a conformational transition in a solvated ring system.