Self-consistent phonons: An accurate and practical method to account for anharmonic effects in equilibrium properties of general classical or quantum many-body systems

Abstract

The self-consistent phonons (SCP) method is a practical approach for computing structural and dynamical properties of a general quantum or classical many-body system while incorporating anharmonic effects. However, a convincing demonstration of the accuracy of SCP and its advantages over the standard harmonic approximation is still lacking. Here we apply SCP to classical Lennard-Jones (LJ) clusters and compare with numerically exact results. The close agreement between the two reveals that SCP accurately describes structural properties of the classical LJ clusters from zero-temperature (where the method is exact) up to the temperatures at which the chosen cluster conformation becomes unstable. Given the similarities between thermal and quantum fluctuations, both physically and within the SCP ansatz, the accuracy of classical SCP over a range of temperatures suggests that quantum SCP is also accurate over a range of quantum de Boer parameter Λ=ℏ/(σmε), which describes the degree of quantum character of the system.