Predicting crystal structures of organic compounds

Price, Sarah L.

doi:10.1039/c3cs60279f

Cited by 455 publications

(479 citation statements)

References 51 publications

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“…7,78,276,277 More than half of the compounds in a pharmaceutically relevant data set show polymorphism, 278 and the energy differences between polymorphs are usually less than 1 kcal/mol and often even less than 1 kJ/mol (0.24 kcal/mol). The X23 database contains two polymorphs of oxalic acid, for which the experimental energy difference between the α and β forms amounts to only 0.05 kcal/mol.…”

Section: Benchmark Databasesmentioning

confidence: 99%

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

2017

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Noncovalent van der Waals (vdW) or dispersion forces are ubiquitous in nature and influence the structure, stability, dynamics, and function of molecules and materials throughout chemistry, biology, physics, and materials science. These forces are quantum mechanical in origin and arise from electrostatic interactions between fluctuations in the electronic charge density. Here, we explore the conceptual and mathematical ingredients required for an exact treatment of vdW interactions, and present a systematic and unified framework for classifying the current first-principles vdW methods based on the adiabatic-connection fluctuation−dissipation (ACFD) theorem (namely the Rutgers−Chalmers vdW-DF, Vydrov−Van Voorhis (VV), exchange-hole dipole moment (XDM), Tkatchenko−Scheffler (TS), many-body dispersion (MBD), and random-phase approximation (RPA) approaches). Particular attention is paid to the intriguing nature of many-body vdW interactions, whose fundamental relevance has recently been highlighted in several landmark experiments. The performance of these models in predicting binding energetics as well as structural, electronic, and thermodynamic properties is connected with the theoretical concepts and provides a numerical summary of the state-of-the-art in the field. We conclude with a roadmap of the conceptual, methodological, practical, and numerical challenges that remain in obtaining a universally applicable and truly predictive vdW method for realistic molecular systems and materials.

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Section: Benchmark Databasesmentioning

confidence: 99%

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

2017

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“…5,7,8 Furthermore, in biological applications there can be numerous shallow energy minima with different conformations. Particularly for complex organic systems, predicting the exact lowest energy conformation is crucial to determine the crystal structure of drugs 9,10 and the mechanisms by which proteins function. 11 One particularly interesting weakly interacting system of relevance to potential applications in clean energy, water pua) Electronic mail: angelos.michaelides@ucl.ac.uk rification, hydrogen storage, and bio-sensing, [12][13][14][15][16] is the interaction of water with layered materials.…”

Section: Introductionmentioning

confidence: 99%

Water on BN doped benzene: A hard test for exchange-correlation functionals and the impact of exact exchange on weak binding

Al-Hamdani

Alfè

Lilienfeld

et al. 2014

The Journal of Chemical Physics

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Density functional theory (DFT) studies of weakly interacting complexes have recently focused on the importance of van der Waals dispersion forces, whereas the role of exchange has received far less attention. Here, by exploiting the subtle binding between water and a boron and nitrogen doped benzene derivative (1,2-azaborine) we show how exact exchange can alter the binding conformation within a complex. Benchmark values have been calculated for three orientations of the water monomer on 1,2-azaborine from explicitly correlated quantum chemical methods, and we have also used diffusion quantum Monte Carlo. For a host of popular DFT exchange-correlation functionals we show that the lack of exact exchange leads to the wrong lowest energy orientation of water on 1,2-azaborine. As such, we suggest that a high proportion of exact exchange and the associated improvement in the electronic structure could be needed for the accurate prediction of physisorption sites on doped surfaces and in complex organic molecules. Meanwhile to predict correct absolute interaction energies an accurate description of exchange needs to be augmented by dispersion inclusive functionals, and certain non-local van der Waals functionals (optB88- and optB86b-vdW) perform very well for absolute interaction energies. Through a comparison with water on benzene and borazine (B3N3H6) we show that these results could have implications for the interaction of water with doped graphene surfaces, and suggest a possible way of tuning the interaction energy.

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“…Choosing t 0 = 0 the resulting two-fold superstructure has orthorhombic space group symmetry P2 1 , the width of the maps is 3.5 Å for (x 1 , x 4 ), 2.5 Å for (x 2 , x 4 ) and 3.3 Å for (x 3 , x 4 ). The higher-dimensional Fourier maps are calculated with Jana2006.…”

Section: Discussionmentioning

confidence: 99%

“…It is not properly understood how the short-range intermolecular interactions between neighbouring molecules produces the long-range order in crystals. For example, computational approaches to crystal structures can predict the crystal structures of relatively simple molecular crystals provided these structures possess translational symmetry [1]. However, long range order can be periodic as well as aperiodic, resulting in a modulated crystal structure in the latter case [2][3][4][5][6][7].…”

Section: Introductionmentioning

confidence: 99%