Assessing the performance of density functional theory in optimizing molecular crystal structure parameters

Binns, Jack; Healy, Mary R.; Parsons, Simon; Morrison, Carole A.

doi:10.1107/s205252061303268x

Cited by 31 publications

(33 citation statements)

References 42 publications

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“…The errors are not systematic; the mean errors in lattice vector lengths are merely À0.03 Å and +0.04 Å for the FIT and W99rev6311P5 force fields respectively. PBE-TS reproduces crystal geometries very well, 27,33 but not lattice energies. 34 Of course, an energy model must perform well on both energies and geometries to be useful and a benchmark study really should consider both.…”

Section: Lattice Parameters and Geometriesmentioning

confidence: 95%

Accurate force fields and methods for modelling organic molecular crystals at finite temperatures

Nyman

Pundyke

Day

2016

Phys. Chem. Chem. Phys.

111

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We present an assessment of the performance of several force fields for modelling intermolecular interactions in organic molecular crystals using the X23 benchmark set. The performance of the force fields is compared to several popular dispersion corrected density functional methods. In addition, we present our implementation of lattice vibrational free energy calculations in the quasi-harmonic approximation, using several methods to account for phonon dispersion. This allows us to also benchmark the force fields' reproduction of finite temperature crystal structures. The results demonstrate that anisotropic atom-atom multipole-based force fields can be as accurate as several popular DFT-D methods, but have errors 2-3 times larger than the current best DFT-D methods. The largest error in the examined force fields is a systematic underestimation of the (absolute) lattice energy.

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Section: Lattice Parameters and Geometriesmentioning

confidence: 95%

Accurate force fields and methods for modelling organic molecular crystals at finite temperatures

Nyman

Pundyke

Day

2016

Phys. Chem. Chem. Phys.

111

View full text Add to dashboard Cite

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“…34,35 To avoid this, the proton was also fixed in position in the two problematic optimisations: r1s2-f and r2s2-f. Hydrogen atom-only optimisation was also carried out, but the maximum forces on the heavy atoms were two orders of magnitude larger than optimisation involving all atom positions and the ordering of predicted carbon chemical shift assignments was also found to match poorly with experimental data. The behaviour of the SSHB in 2FS-INA was problematic in the geometry optimisations, with the proton being transferred in some of the calculations.…”

Section: Methodsmentioning

confidence: 99%

A furosemide–isonicotinamide cocrystal: an investigation of properties and extensive structural disorder

et al. 2015

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Furosemide is a loop diuretic drug marketed in solid form which suffers from low solubility and low permeability. The pharmaceutically relevant properties of a recently described furosemide-isonicotinamide 2:1 cocrystal (2FS-INA) were investigated and compared with those of other known furosemide cocrystals. The intrinsic dissolution rate of 2FS-INA was found to be very similar to that of commercial FS, while its equilibrium solubility was 5.6 times higher than that of pure FS. The extensive structural disorder in 2FS-INA observed by diffraction methods was also investigated by variabletemperature solid-state NMR in conjunction with first principles calculations. 15 N NMR confirmed the absence of proton disorder in the short OH⋅⋅⋅N hydrogen bond. The disordered sulphonamide group was found to be dynamic by variable temperature 2 H experiments, involving fast exchange of the sulphonamide NH2 protons combined with a rotation of the whole sulphonamide group about the C-S bond. The disorder of the furan rings of both the unique furosemide molecules was also found to be dynamic by 13 C experiments, with roughly the same activation barrier for both rings.Please do not adjust margins Please do not adjust margins recycle delay of 1 second in the direct excitation experiment and 10-35 s in the CP experiments, depending on temperature. The contact time was 4 ms, acquiring over 48-180 transients. SPINAL64 with 78 kHz

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“…Rietveld refinements of the structure of ε-glycine were carried-out using TOPAS-Academic (Coelho, 2005) starting from the coordinates in ref. 37 All non-hydrogen atoms were refined with a common isotropic thermal parameter and the displacement parameters of the D-atoms were set equal to 1.5 times this value. Lead, tungsten carbide and nickel were also included in the refinement models.…”

Section: Structure Solution and Refinementmentioning

confidence: 99%

How focussing on hydrogen bonding interactions in amino acids can miss the bigger picture: a high-pressure neutron powder diffraction study of ε-glycine

et al. 2015

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The crystal structures of amino acids, which are composed of molecules in their zwitterionic tautomers, are usually interpreted in terms of strong NH⋯O hydrogen bond formation between the ammonium and carboxylate groups supported by weaker dispersion or CH⋯O interactions. This view of the factors which promote thermodynamic stability in the crystalline amino acids has been re-examined in two phases of glycine, the trigonal γ-form, which is the thermodynamically most stable form under ambient conditions, and the ε-form, which is generated from γ-glycine at high pressure. A combination of Hirshfeld surface analysis, periodic DFT, PIXEL and symmetry-adapted perturbation theory calculations indicates that the conventional interpretation of intermolecular interactions in crystalline amino acids phases fails to recognise the over-whelming significance of Coulombic attraction and repulsion. There are no intermolecular interactions in either phase that can plausibly be described as dispersion-based. The interaction energies of molecules connected by so-called CH⋯O H-bonds are far in excess of accepted values for such interactions. Of the 14 closest intermolecular contacts in both phases, six have destabilizing interaction energies:in γ-glycine a hydrogen bond with 'text-book' NH⋯O contact geometry is part of a destabilising molecule-molecule interaction. The relative stabilities of the phases are best understood not in terms of a series of stabilising atom-atom contacts, but rather as a balance between efficient filling of space in the highpressure ε-phase, and more weakly repulsive electrostatic whole-molecule interactions in the γ-phase. CrystEngCommThis journal is

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Assessing the performance of density functional theory in optimizing molecular crystal structure parameters

Cited by 31 publications

References 42 publications

Accurate force fields and methods for modelling organic molecular crystals at finite temperatures

Accurate force fields and methods for modelling organic molecular crystals at finite temperatures

A furosemide–isonicotinamide cocrystal: an investigation of properties and extensive structural disorder

How focussing on hydrogen bonding interactions in amino acids can miss the bigger picture: a high-pressure neutron powder diffraction study of ε-glycine

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