Long-range interactions of aromatic molecules with alkali-metal and alkaline-earth-metal atoms.

This article focuses on the first-principles calculation of long-range intermolecular interaction coefficients for complexes formed by small aromatic molecules (benzene, pyridine, furan, and pyrrole) and alkali-metal (Li, Na, K, Rb, Cs) or alkaline-earth-metal (Be, Mg, Ca, Sr, Ba) atoms in their electronic ground states. Using a combination of analytical wavefunctions, coupled cluster theory, and density functional theory (DFT) response methods, the study computes isotropic and anisotropic dispersion and induction coefficients up to order n = 12, demonstrating that inclusion of terms beyond n = 6 is essential for accurately describing interaction energies near the van der Waals region (~6 Å). The resulting long-range potentials are intended to support the construction of comprehensive potential energy surfaces for spectroscopic, scattering, and ultracold physics applications, including sympathetic cooling and controlled chemical reactions of polyatomic molecules with ultracold metal atoms. Supplementary materials provide computational routines and extensive data sets for polarizabilities, multipole moments, and interaction coefficients relevant to these complexes.