Ab initio study of the interaction between the charged system (FH+) and the He atom

Abstract

We investigated the molecular structure and spectroscopic properties of the charged system (FH⁺) in interaction with a helium atom using an ab initio quantum chemistry approach in Jacobi coordinates. Our study focused on the ground state X²Π of (FH⁺) with various theoretical methods including UCCSD, UCCSD(T) and UCCSD(T)-F12, alongside basis sets like aug-cc-pVnZ (n = T, Q, 5, and 6) and cc-pVQZ-F12. We evaluated how these methods and basis sets affect the minimum energies We assessed the impact of the methods, basis sets, and extrapolation approaches on the minimum energies. Potential energy surfaces (PES) were generated using the correlated UCCSD(T)-F12 method with cc-pVQZ-F12 for hydrogen and fluorine, and cc-pVQZ-F12/optri for helium. These surfaces, considering spin-orbit coupling, are degenerate for linear geometries (θ=0° and θ=180°) of the (FH+)-He complex and correlate with the doubly degenerate X²Π state of (FH⁺). Our results reveal a strong anisotropic character at short and intermediate distances and a quasi-isotropic character upon dissociation into FH⁺ and He. We compared the spectroscopic parameters of the (FH⁺)-He complex with existing theoretical data, finding that the linear arrangement exhibits the highest stability, consistent with previous results for similar complexes. This conclusion is supported by the Milliken atomic charge distribution and a three-dimensional map of the Molecular Electrostatic Potential. Additionally, we used the LEVEL program, to calculate the bound rovibronic levels of the (FH⁺)-He complex for angular momentum values Ω=1/2 and Ω=3/2. Utilizing our ab initio results and a general interpolation approach based on the Reproducing Kernel Hilbert Space method, we generated contour maps illustrating the analytical potential for the (FH⁺)-He system. These findings will be employed to study the stabilities, geometries, energetics, and structures of the FH⁺ charged system within helium clusters.