Perturbation method to calculate the density of states

TL;DR

This paper introduces a perturbation-based Monte Carlo method to compute the density of states and related thermodynamic properties by relating ensemble averages of switching probabilities between Hamiltonians, demonstrating its effectiveness on various systems.

Contribution

The paper presents a novel Monte Carlo perturbation approach to calculate the density of states, enabling efficient estimation of thermodynamic properties across different systems.

Findings

Higher convergence rate than Wang-Landau sampling in tested cases

Successfully computed vapor pressure of an anharmonic Einstein crystal

Determined the energy dependence of DOS ratios for complex systems

Abstract

Monte Carlo switching moves ("perturbations") are defined between two or more classical Hamiltonians sharing a common ground-state energy. The ratio of the density of states (DOS) of one system to that of another is related to the ensemble averages of the microcanonical acceptance probabilities of switching between these Hamiltonians, analogously to the case of Bennett's acceptance ratio method for the canonical ensemble [C. H. Bennett, J. Comput. Phys., 22, 245 (1976)]. Thus, if the DOS of one of the systems is known, one obtains those of the others and, hence, the partition functions. As a simple test case, the vapor pressure of an anharmonic Einstein crystal is computed, using the harmonic Einstein crystal as the reference system in one dimension; an auxiliary calculation is also performed in three dimensions. As a further example of the algorithm, the energy dependence of the ratio of the DOS of the square-well and hard-sphere tetradecamers is determined, from which the temperature dependence of the constant-volume heat capacity of the square-well system is calculated and compared with canonical Metropolis Monte Carlo estimates. For these cases and reference systems, the perturbation calculations exhibit a higher degree of convergence per Monte Carlo cycle than Wang-Landau (WL) sampling, although for the one-dimensional oscillator the WL sampling is ultimately more efficient for long runs. Last, we calculate the vapor pressure of liquid gold using an empirical Sutton-Chen many-body potential and the ideal gas as the reference state. Although this proves the general applicability of the method, by its inherent perturbation approach, the algorithm is suitable for those particular cases where the properties of a related system are well known.