Molecular Thermodynamics of Quantum Fluids using a Thermodynamic Path-Integral Perturbation Theory

We present a semiclassical thermodynamic perturbation theory for quantum fluids (1) based on the exact analogy between the discretized path-integral formalism of Quantum Mechanics and the partition function of a classical... [ view full abstract ]

We present a semiclassical thermodynamic perturbation theory for quantum fluids (1) based on the exact analogy between the discretized path-integral formalism of Quantum Mechanics and the partition function of a classical system composed of necklace molecules (2). A Zwanzig expansion is obtained using a quantum hard spheres as a reference fluid. Combining path integral Monte Carlo computer simulations and equations of state for classical fluids derived from the SAFT approach, results are presented for perturbation terms and thermodynamic properties of systems interacting with square-well and Mie pair potentials. Applications to hydrogen and deuterium in bulk and confined phases are discussed.

We acknowledge support from the University of Guanajuato, grant 1,143/2016 .

1. C. Serna, A. Gil-Villegas, Mol. Phys. 114, 2700 (2016).
2. D. Chandler, P. G. Wolynes, J. Chem. Phys. 74, 4078 (1981).