Theory of chemical reactions of vibronically excited H2 (B 1Σ+u). III. Formation of bound excited states of the (H2)2, (H2)3, and (H2)5 clusters

Abstract

We present a simple theory of bonding in certain van der Waals clusters and results of configuration‐interaction calculations which demonstrate the existence of bound excited singlet states of the (H₂)₂, (H₂)₃, and (H₂)₅ clusters. The hypersurfaces of these bound states have minima close to avoided crossings with the lowest ¹A′ state repulsive hypersurfaces. Similar results are expected for a variety of other clusters. Apart from their importance in the theory and spectroscopy of molecular structure and dynamics, these findings may find application in problems of excitation and energy transfer in liquids and solids, whose properties are supposed to be approximated by large clusters.