Internal‐to‐Cartesian back transformation of molecular geometry steps using high‐order geometric derivatives

In geometry optimizations and molecular dynamics calculations, it is often necessary to transform a geometry step that has been determined in internal coordinates to Cartesian coordinates. A new method for performing such transformations, the high‐order path‐expansion (HOPE) method, is here presented. The new method treats the nonlinear relation between internal and Cartesian coordinates by means of automatic differentiation. The method is reliable, applicable to any system of internal coordinates, and computationally more efficient than the traditional method of iterative back transformations. As a bonus, the HOPE method determines not just the Cartesian step vector but also a continuous step path expressed in the form of a polynomial, which is useful for determining reaction coordinates, for integrating trajectories, and for visualization. © 2013 Wiley Periodicals, Inc.

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