Barnes Update Applied in the Gauss–Newton Method: An Improved Algorithm to Locate Bond Breaking Points

• Published in: Journal of chemical theory and computation Vol. 17; no. 2; pp. 996 - 1007
• Main Authors: Bofill, Josep Maria, Valero, Rosendo, Ribas-Ariño, Jordi, Quapp, Wolfgang
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 09.02.2021
• Subjects: Algorithms; Chemical reactions; Critical point; Eigenvectors; Hessian matrices; Jacobi matrix method; Jacobian matrix; Mathematical analysis; Newton methods; Optimization; Perturbation; Potential energy; Reaction Mechanisms
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.0c00910

A mechanochemical reaction is a reaction induced by mechanical energy. A general accepted model for this type of reaction consists of a first-order perturbation on the associated potential energy surface (PES) of the unperturbed molecular system due to mechanical stress or pulling force. Within this theoretical framework, the so-called optimal barrier breakdown points or optimal bond breaking points (BBPs) are critical points of the unperturbed PES where the Hessian matrix has a zero eigenvector that coincides with the gradient vector. Optimal BBPs are “catastrophe points” that are particularly important because their associated gradient indicates how to optimally harness tensile forces to induce reactions by transforming a chemical reaction into a barrierless process. Building on a previous method based on a nonlinear least-squares minimization to locate BBPs (Bofill et al., J. Chem. Phys. 2017, 147, 152710-10), we propose a new algorithm to locate BBPs of any molecular system based on the Gauss–Newton method combined with the Barnes update for a nonsymmetric Jacobian matrix, which is shown to be more appropriate than the Broyden update. The efficiency of the new method is demonstrated for a multidimensional model PES and two medium size molecular systems of interest in enzymatic catalysis and mechanochemistry.