![]() ![]() Clausius’ virial theorem set a basis for relating kinetic energy in a body of independent material particles to its potential energy, pointing to their complementary role with respect to the second law of maximum entropy. Furthermore, the corrected partition function also overcomes technical difficulties and leads to an increased stability of the calculations in regard to the size of the cluster set. Our intention is to provide easy methods for estimating entropy and chemical potentials for gas phase reactions. ![]() The effect of the corrected partition function is visible in the different populations of clusters, which become physically more meaningful in that larger clusters are higher populated in the liquid phase and the gas phase is mainly populated by the monomers. The contribution to the entropy of a system by each aspect of the system which is in internal thermodynamic equilibrium tends to zero as T to 0. The enthalpies and entropies of vaporization show improvements from 6.5 error to 3.3 kJ mol −1 deviation to experiment and from 28.4 error to 13.5 J mol −1 K −1 deviation to experiment, respectively. The new scheme is tested on a set of nine organic solvents for the calculation of the enthalpy and entropy of vaporization. ![]() Here, the low energy vibrational frequencies in the vibrational partition function are treated as hindered rotations instead of vibrations. The changes are based on a previously suggested modification of the molecular entropy calculation in the gas phase. In this work, we present an altered partition function that leads to an improved calculation of the enthalpy and entropy of vaporization in the framework of quantum cluster equilibrium theory. ![]()
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