Quantum dynamics of clusters on experimental potential energy surfaces: Triplet and quintet O2‐O2 surfaces and dimers of para‐N2 with ortho‐ and para‐N2 and with O2

Abstract

AbstractThe potential energy surfaces for the dimers of the major components of the atmosphere had been previously characterized through a combined analysis of scattering experiments and second virial coefficient data and represented as a spherical harmonic expansion functional form, which permits us to describe the intermolecular features in the salient geometries of the complexes and account for the relative contributions arising from interaction components of different nature. The present quantum mechanical calculations on these surfaces extend our studies aimed at the full characterization of structure and internal dynamics of the clusters. Bound states and eigenfunctions are obtained. Here, we consider specific aspects of excited electronic states (such as the O2‐O2 triplet and quintet surfaces) and odd–odd and even–odd rotovibrational combination of levels of the N2‐N2 dimer, and the odd–odd combination for the N2‐O2 system, providing a guidance for the analysis of spectra of interest for atmospheric monitorings. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004