Ridge method for finding saddle points on potential energy surfaces

摘要: A new method is proposed for locating saddle points on potential energy surfaces. The involves walking the ridge separating reactants’ and products’ valleys toward its minimum, which a point in coordinate space. Of particular advantage ab initio calculations, does not require evaluation of second derivatives energy. Another important feature that no assumptions about transition state geometry are needed, it easy to impose linear constraints molecular structure. supplemented by heuristic detour algorithm, enables one deal with unfortunate choices coordinates. Both algorithms illustrated several examples where complexity surface ranges from simple analytical formula numerical many‐body potential.