Quantum anharmonic densities of states using the Wang–Landau method

The Wang-Landau sampling method is adapted to the calculation of quantum densities of states for fully coupled anharmonic systems. The accuracy of the method is illustrated against exact counting for two molecules with separable oscillators, namely, the Zundel complex H(5)O(2) (+) and the Na(11) cluster. Application to the fully coupled naphthalene molecule (C(10)H(8)) reveals significant deviations in the finite temperature thermodynamical properties that are not captured by simple perturbation theory. There are no limitations in the size of the molecules that can be treated with this method.