Two Faces of the Two Phase Thermodynamic Model

The quantum harmonic model and the two-phase thermodynamics method (2PT) are widely used to obtain quantum corrected properties such as isobaric heat capacities or molar entropies. 2PT heat capacities were calculated inconsistently in the literature. For water the classical heat capacity was also considered, but for organic liquids it was omitted. We reanalyzed the performance of different quantum corrections on the heat capacities of common organic solvents against experimental data. We have pointed out serious flaws in previous 2PT studies. The vibrational density of states was calculated incorrectly causing 39 % relative error in diffusion coefficients and 45 % error in the 2PT heat capacities. The wrong conversion of isobaric isochoric heat capacity also caused about 40 % error but in the other direction. We have introduced the concept of anharmonic correction (AC) which is simply the deviation of the classical heat capacity from that of the harmonic oscillator model. This anharmonic contribution is around +30-40 J/mol/K for water depending on the water model and -8-10 J/mol/K for hydrocarbons and halocarbons. AC is unrealistically large, +40 J/K/mol for alcohols and amines indicating some deficiency of the OPLS force field. The accuracy of the computations was also assessed with the determination of the self-diffusion coefficients.

Two Faces of the Two Phase Thermodynamic Model

<div>The quantum harmonic model and the two-phase thermodynamics method (2PT) are widely used to obtain quantum corrected properties such as isobaric heat capacities or molar entropies. 2PT heat capacities were calculated inconsistently in the literature. For water the classical heat capacity was also considered, but for organic liquids it was omitted. We reanalyzed the performance of different quantum corrections on the heat capacities of common organic solvents against experimental data. We have pointed out serious flaws in previous 2PT studies. The vibrational density of states was calculated incorrectly causing 39 \% relative error in diffusion coefficients and 45 \% error in the 2PT heat capacities. The wrong conversion of isobaric isochoric heat capacity also caused about 40 \% error but in the other direction. We have introduced the concept of anharmonic correction which is simply the deviation of the classical heat capacity from that of the harmonic oscillator model. This anharmonic contribution is around +30-40 J/mol/K for water depending on the water model and -8-10 J/mol/K for hydrocarbons and halocarbons. AC is unrealistically large, +40 J/K/mol for alcohols and amines indicating some deficiency of the OPLS force field. The accuracy of the computations was also assessed with the determination of the self-diffusion coefficients.<br></div>