To investigate the performance of quasi-harmonic electronic structure methods for modeling molecular crystals at finite temperatures and pressures, thermodynamic properties are calculated for the low-temperature α polymorph of crystalline methanol. Both density functional theory (DFT) and ab initio wavefunction techniques up to coupled cluster theory with singles, doubles, and perturbative triples (CCSD(T)) are combined with the quasi-harmonic approximation to predict energies, structures, and properties. The accuracy, reliability, and uncertainties of the individual quantum-chemical methods are assessed via detailed comparison of calculated and experimental data on structural properties (density) and thermodynamic properties (isobaric heat capacity). Performance of individual methods is also studied in context of the hierarchy of the quantum-chemical methods. The results indicate that while some properties such as the sublimation enthalpy and thermal expansivity can be modeled fairly well, other properties such as the molar volume and isobaric heat capacities are harder to predict reliably. The errors among the energies, structures, and phonons are closely coupled, and most accurate predictions here appear to arise from fortuitous error compensation among the different contributions. This study highlights how sensitive molecular crystal property predictions can be to the underlying model approximations and the significant challenges inherent in first-principles predictions of solid state structures and thermochemistry.

Department of Chemistry University of California Riverside California 92521 USA

Department of Physical Chemistry University of Chemistry and Technology Prague Technická 5 CZ 166 28 Prague 6 Czech Republic

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Ab initio prediction of the polymorph phase diagram for crystalline methanol