A four-dimensional potential energy surface for the He - HCN complex

TL;DR

This paper develops a detailed four-dimensional potential energy surface for the He-HCN complex, enabling accurate predictions of rovibrational energy levels and collision dynamics, validated against experimental and previous theoretical data.

Contribution

It introduces a new four-dimensional potential energy surface for He-HCN, incorporating vibrational bending, with high-level ab initio calculations and accurate fitting, improving upon previous models.

Findings

Global minimum at 7.94 Å with 30.35 cm^-1 well depth

Calculated dissociation energy of 8.99 cm^-1 closely matches experimental 9.42 cm^-1

Good agreement with experimental rovibrational and collision data

Abstract

A four-dimensional potential energy surface for the interaction between He and HCN with vibrational bending is presented. Ab initio calculations were carried out at the coupled-cluster level with single and double excitations and a perturbative treatment of triple excitations, using a quadruple-zeta basis set and mid-bond functions. An accurate fit to the Ab-initio data has been obtained with a parametrized functional form. The global minimum is found in the linear He-HCN configuration with the H atom pointing towards Helium at the intermolecular separation of 7.94 a0. The corresponding well depth is 30.35 cm^-1 . The quality of the new potential has been tested by performing two comparisons with previous theoretical and experimental works. First, the rovibrational energy levels of the He-HCN complex for a linear configuration of the HCN molecule have been calculated. The dissociation energy is 8.99 cm^-1, which is slightly smaller than the semi-empirical value of 9.42 cm^-1 . The transitions frequencies are found to be in good agreement with the experimental data. Second, we performed close coupling calculations of the rotational de-excitation of HCN in collisions with He and observed a close similarity with the theoretical data published in a recent study.