Thermal dissociation of dipositronium: path integral Monte Carlo approach

Abstract

Path integral Monte Carlo simulation of the dipositronium "molecule" Ps${}_2$ reveals its surprising thermal instability. Although, the binding energy is $\sim 0.4$ eV, due to the strong temperature dependence of its free energy Ps${}_2$ dissociates, or does not form, above $\sim 1000$ K, except for high densities where a small fraction of molecules are in equilibrium with Ps atoms. This prediction is consistent with the recently reported first observation of stable Ps${}_2$ molecules by Cassidy & Mills Jr., Nature {\bf 449}, 195 (07), and Phys.Rev.Lett. {\bf 100}, 013401 (08); at temperatures below 1000 K. The relatively sharp transition from molecular to atomic equilibrium, that we find, remains to be experimentally verified. To shed light on the origin of the large entropy factor in free energy we analyze the nature of interatomic interactions of these strongly correlated quantum particles. The conventional diatomic potential curve is given by the van der Waals interaction at large distances, but due to the correlations and high delocalization of constituent particles the concept of potential curve becomes ambiguous at short atomic distances.

Submitted to the Physical Review Letters

References in corpus (1)

• Hydrogen molecule ion: Path integral Monte Carlo approach

Cited by in corpus (4)

• Simulations of Trions and Biexcitons in Layered Hybrid Organic-Inorganic Lead Halide Perovskites
• Finite temperature quantum statistics of H${}_3^{+}$ molecular ion
• Path Integrals: From Quantum Mechanics to Photonics
• Density Matrix Renormalization Group Study of a One Dimensional Diatomic Molecule beyond the Born-Oppenheimer Approximation