Full-Dimensional Global Potential Energy Surface for the KRb + KRb → K2Rb2* → K2 + Rb2 Reaction with Accurate Long-Range Interactions and Quantum Statistical Calculation of the Product State Distribution under Ultracold Conditions.

A full-dimensional global potential energy surface (PES) for the KRb + KRb → K2Rb2* → K2 + Rb2 reaction is reported based on high-level ab initio calculations. The short-range part of the PES is fit with the permutationally invariant polynomial-neural network method, while the long-range parts of the PES in both the reactant and product asymptotes are represented by an asymptotically correct form. The long- and short-range parts are connected with intermediate-range parts to make them smooth. Within a statistical quantum model, this PES reproduces both the measured loss rates of ultracold KRb molecules and the K2 and Rb2 product state distributions, underscoring the important role of tunneling in ultracold chemistry. The PES also correctly predicts the lifetime of the K2Rb2* intermediate complex within the Rice-Ramsperger-Kassel-Marcus limit. It thus provides a reliable platform for future dynamical studies of the prototypical reaction.