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

ABSTRACT: 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-(

SUBMITTER: Yu Y 

PROVIDER: S-EPMC12569676 | biostudies-literature | 2025 Oct

REPOSITORIES: biostudies-literature