Two New Methods To Generate Internal Coordinates for Molecular Wave Packet Dynamics in Reduced Dimensions

J. Chem. Theory Comput., 2016, 12 (12), pp 5698–5708

J.Chem.Theory Comput.

The curse of dimensionality still remains as the central challenge of molecular quantum dynamical calculations. Either compromises on the accuracy of the potential landscape have to be made or methods must be used that reduce the dimensionality of the configuration space of molecular systems to a low dimensional one. For dynamic approaches such as grid-based wave packet dynamics that are confined to a small number of degrees of freedom this dimensionality reduction can become a major part of the overall problem. A common strategy to reduce the configuration space is by selection of a set of internal coordinates using chemical intuition. We devised two methods that increase the degree of automation of the dimensionality reduction as well as replace chemical intuition by more quantifiable criteria. Both methods reduce the dimensionality linearly and use the intrinsic reaction coordinate as guidance. The first one solely relies on the intrinsic reaction coordinate (IRC), whereas the second one uses semiclassical trajectories to identify the important degrees of freedom.

TU München