Long-Range Interaction between Molecules with Electronic Degeneracy: Beyond the Born–Oppenheimer Approximation

Long-range intermolecular interaction plays an essential
role in
(ultra)cold collisions. For monomers with degenerate electronic states,
an accurate description of the long-range interaction can be challenging
due to the potential breakdown of the Born–Oppenheimer approximation.
In this work, we developed a general method to construct long-range
interaction potential energy surfaces (IPESs) between arbitrary molecules
using the degenerate perturbation theory of Schrödinger. To
further simplify the application of this method, a group-theoretical
method is introduced to identify nonzero components of electrostatic
properties of monomers, especially for the nonlinear molecules. To
demonstrate this approach, we report the long-range IPESs of the O(3P)–OH(2Π) and OH(2Π)–OH(2Π) systems. The excellent agreement with ab
initio calculations in large separations, even near electronic
degeneracies, confirms the accuracy of our approach. The method is
expected to lay the groundwork for the accurate investigation of (ultra)cold
collisional dynamics involving open-shell species.