On the use of different coordinate systems in mechanochemical force analyses.

Abstract

Force analyses are crucial for a comprehensive understanding of mechanochemical processes. The choice of coordinate system in these kinds of analyses is a nontrivial task that determines the quality and validity of the obtained results. Here, we study the suitability of different sets of coordinates for mechanical force analyses, i.e., normal modes, delocalized internal, redundant internal, and Z-matrix coordinates. After discussing the theoretical foundations of force analyses using different coordinate systems, we investigate a number of test molecules. We show that normal modes and Z-matrix coordinates deliver useful results only if certain requirements are fulfilled and that only redundant internal coordinates yield meaningful results in all cases.