Three-body potential energy surface for para-hydrogen

We present a 3D isotropic ab initio three-body (para-H₂)₃ interaction potential energy surface (PES). The electronic structure calculations are carried out at the correlated coupled-cluster theory level, with single, double, and perturbative triple excitations. The calculations use an augmented correlation-consistent triple zeta basis set and a supplementary midbond function. We construct the PES using the reproducing-kernel Hilbert space toolkit [O. T. Unke and M. Meuwly, J. Chem. Inf. Model. 57, 1923 (2017)] with phenomenological and empirical adjustments to account for short-range and long-range behaviors. The (para-H₂)₃ interaction energies deviate drastically from the Axilrod-Teller-Muto (ATM) potential at short intermolecular separations. We find that the configuration of three para-H₂ molecules at the corners of an equilateral triangle is responsible for the majority of the (para-H₂)₃ interaction energy contribution in a hexagonal-close-packed lattice. In cases where two para-H₂ molecules are close to one another while the third is far away, the (para-H₂)₃ interaction PES takes the form of a modified version of the ATM potential. We expect the combination of this PES together with a first-principles para-H₂-para-H₂ adiabatic hindered rotor potential to outperform a widely used effective pair potential for condensed many-body systems of para-H₂.