Reaction path following in mass-weighted internal coordinates

Our previous algorithm for following reaction paths downhill (J. Chem. Phys. 1989, 90, 2154), has been extended to use mass-weighted internal coordinates. Points on the reaction path are round by constrained optimizations involving the internal degrees or freedom or the molecule. The points are optimized so that the segment or the reaction path between any two adjacent points is described by an arc or a circle in mass-weighted internal coordinates, and so that the gradients (in mass-weighted internals) at the end points or the arc are tangent to the path. The algorithm has the correct tangent vector and curvature vectors in the limit or small step size but requires only the transition vector and the energy gradients; the resulting path is continuous, differentiable, and piecewise quadratic