Spherical and hyperspherical representation of potential energy surfaces for intermolecular interactions

Abstract

AbstractThe definition of a proper set of coordinates is desirable for the representation of the potential energy surfaces that accounts faithfully also for the symmetry properties of the systems. The expansion in harmonics corresponding to spherical and hyperspherical mapping for atomic and molecular interactions is considered in the present article. The choice of a few but significant configurations, “leading configurations,” relies upon considerations about the geometrical features of the systems. Their minimal number depends on the symmetry property and on the number of coordinates of the problem, and allows us to determine the expansion moments of the interaction potentials, to be used for bound state and dynamical calculations. Here, we report an outlook of prescriptions for the choice of leading configurations, which provides the expansion of the potential energy surface for interacting closed shell systems, such as linear‐molecule–linear‐molecule, floppy‐molecule–rare‐gas‐atom, and nonlinear‐molecule–linear‐molecule. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011