Beyond Born–Oppenheimer Constructed Diabatic Potential Energy Surfaces for HeH₂⁺

Abstract

First-principles based beyond Born–Oppenheimer theory has been employed to construct multistate global Potential-Energy Surfaces (PESs) for the HeH₂⁺ system by explicitly incorporating the Nonadiabatic Coupling Terms (NACTs). Adiabatic PESs and NACTs for the lowest four electronic states (1²A’, 2²A’, 3²A’ and 4²A’) are evaluated as functions of hyperangles for a grid of fixed values of the hyperradius in hyperspherical coordinates. Conical intersection between different states are validated by integrating the NACTs along appropriately chosen contours. Subsequently, adiabatic-to-diabatic (ADT) transformation angles are determined by solving the ADT equations to construct the diabatic potential matrix for the HeH₂⁺ system which are smooth, single-valued, continuous, and symmetric and are suitable for performing accurate scattering calculations for the titled system.