Conformational polymorphs of organic molecular crystals represent a challenging test for quantum chemistry because they require careful balancing of the intra- and intermolecular interactions. This study examines 54 molecular conformations from 20 sets of conformational polymorphs, along with the relative lattice energies and 173 dimer interactions taken from six of the polymorph sets. These systems are studied with a variety of van der Waals-inclusive density functionals theory models; dispersion-corrected spin-component-scaled second-order Møller–Plesset perturbation theory (SCS-MP2D); and domain local pair natural orbital coupled cluster singles, doubles, and perturbative triples [DLPNO-CCSD(T)]. We investigate how delocalization error in conventional density functionals impacts monomer conformational energies, systematic errors in the intermolecular interactions, and the nature of error cancellation that occurs in the overall crystal. The density functionals B86bPBE-XDM, PBE-D4, PBE-MBD, PBE0-D4, and PBE0-MBD are found to exhibit sizable one-body and two-body errors vs DLPNO-CCSD(T) benchmarks, and the level of success in predicting the relative polymorph energies relies heavily on error cancellation between different types of intermolecular interactions or between intra- and intermolecular interactions. The SCS-MP2D and, to a lesser extent, ωB97M-V models exhibit smaller errors and rely less on error cancellation. Implications for crystal structure prediction of flexible compounds are discussed. Finally, the one-body and two-body DLPNO-CCSD(T) energies taken from these conformational polymorphs establish the CP1b and CP2b benchmark datasets that could be useful for testing quantum chemistry models in challenging real-world systems with complex interplay between intra- and intermolecular interactions, a number of which are significantly impacted by delocalization error.
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14 March 2022
Research Article|
March 14 2022
The interplay of intra- and intermolecular errors in modeling conformational polymorphs
Special Collection:
Beyond GGA Total Energies for Solids and Surfaces
Gregory J. O. Beran
;
Gregory J. O. Beran
a)
1
Department of Chemistry, University of California
, Riverside, California 92521, USA
a)Author to whom correspondence should be addressed: [email protected]
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Sarah E. Wright;
Sarah E. Wright
2
Department of Chemical Engineering and Analytical Science, University of Manchester
, Manchester, United Kingdom
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Chandler Greenwell
;
Chandler Greenwell
1
Department of Chemistry, University of California
, Riverside, California 92521, USA
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Aurora J. Cruz-Cabeza
Aurora J. Cruz-Cabeza
2
Department of Chemical Engineering and Analytical Science, University of Manchester
, Manchester, United Kingdom
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a)Author to whom correspondence should be addressed: [email protected]
Note: This paper is part of the JCP Special Topic on Beyond GGA Total Energies for Solids and Surfaces.
J. Chem. Phys. 156, 104112 (2022)
Article history
Received:
November 14 2021
Accepted:
February 21 2022
Citation
Gregory J. O. Beran, Sarah E. Wright, Chandler Greenwell, Aurora J. Cruz-Cabeza; The interplay of intra- and intermolecular errors in modeling conformational polymorphs. J. Chem. Phys. 14 March 2022; 156 (10): 104112. https://doi.org/10.1063/5.0088027
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