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How important is thermal expansion for predicting molecular crystal structures and thermochemistry at finite temperatures?
Author(s) -
Heit Yonaton N.,
Beran Gregory J. O.
Publication year - 2016
Publication title -
acta crystallographica section b
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.604
H-Index - 33
ISSN - 2052-5206
DOI - 10.1107/s2052520616005382
Subject(s) - thermochemistry , thermal expansion , thermodynamics , enthalpy , chemistry , gibbs free energy , perturbation theory (quantum mechanics) , cluster expansion , sublimation (psychology) , thermal , enthalpy of sublimation , physics , quantum mechanics , psychology , psychotherapist
Molecular crystals expand appreciably upon heating due to both zero‐point and thermal vibrational motion, yet this expansion is often neglected in molecular crystal modeling studies. Here, a quasi‐harmonic approximation is coupled with fragment‐based hybrid many‐body interaction calculations to predict thermal expansion and finite‐temperature thermochemical properties in crystalline carbon dioxide, ice Ih, acetic acid and imidazole. Fragment‐based second‐order Möller–Plesset perturbation theory (MP2) and coupled cluster theory with singles, doubles and perturbative triples [CCSD(T)] predict the thermal expansion and the temperature dependence of the enthalpies, entropies and Gibbs free energies of sublimation in good agreement with experiment. The errors introduced by neglecting thermal expansion in the enthalpy and entropy cancel somewhat in the Gibbs free energy. The resulting ∼ 1–2 kJ mol −1 errors in the free energy near room temperature are comparable to or smaller than the errors expected from the electronic structure treatment, but they may be sufficiently large to affect free‐energy rankings among energetically close polymorphs.