On the quadratic reaction path evaluated in a reduced potential energy surface model and the problem to locate transition states

✍ Scribed by Josep Maria Anglada; Emili Besalú; Josep Maria Bofill; Ramon Crehuet

• Publisher: John Wiley and Sons
• Year: 2001
• Tongue: English
• Weight: 334 KB
• Volume: 22
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/1096-987x(200103)22:4<387::aid-jcc1010>3.0.co;2-r

✦ Synopsis

Knowledge of the location of saddle points is crucial to the study the chemical reactivity. Using a path following method defined in a reduced potential energy surface, and starting at either the reactant or product region, we propose an algorithm that locates the corresponding saddle point. The reduced potential energy surface is defined by the set of molecular geometry parameters, namely bond distances, bond angles, and dihedral angles that undergo the largest change for the reaction under consideration; the rest of the coordinates are forced to have a null gradient. Consequently, the proposed method can be seen as a new formulation of the distinguished coordinate method. The method is based on a quadratic model; consequently, it only requires the calculation of the energy and the gradient. The Hessian matrix is normally updated except in the first step and the steps where the resulting updated Hessian matrix is not adequate. Some examples are presented and analyzed.