References of "Hoja, Johannes 50022331"
     in
Bookmark and Share    
Full Text
See detailFirst-Principles Modeling of Molecular Crystals: Crystal Structure Prediction and Vibrational Properties
Hoja, Johannes UL

Doctoral thesis (2018)

Understanding the structure and stability, as well as response properties of molecular crystals at certain thermodynamic conditions is crucial for the engineering of new molecular materials and the design ... [more ▼]

Understanding the structure and stability, as well as response properties of molecular crystals at certain thermodynamic conditions is crucial for the engineering of new molecular materials and the design of pharmaceuticals. A reliable description of the polymorphic energy landscape of a molecular crystal would provide an extensive insight into the development of drugs in terms of the existence and the likelihood of late-appearing polymorphs. Furthermore, accurate modeling of low-frequency vibrational spectra would be important for the characterization of molecular crystal polymorphs. However, an accurate description of molecular crystals is very challenging since many properties highly depend on the crystal-packing arrangement of the involved molecules and the temperature. The difficulties for computational predictions of molecular crystal polymorphs lie in the high dimensionality of crystallographic and conformational space, and the need for very accurate relative free energies. It was shown that accurate lattice energies can be obtained by using density-functional theory (DFT) calculations supplemented by a high-level model for long-range van der Waals (vdW) dispersion interactions, such as the many-body dispersion (MBD) model. Therefore, this thesis utilizes throughout vdW-inclusive DFT using the MBD and the related pairwise Tkatchenko-Scheffler (TS) dispersion model and the importance of dispersion interactions is highlighted for several properties. A hierarchical stability-ranking approach based on the DFT+MBD framework for the final stage of a molecular crystal structure prediction procedure is presented and analyzed. This approach provides excellent stability rankings over the diverse set of molecular crystals studied in the latest blind test of the Cambridge Crystallographic Data Centre. The results suggest that accounting for many-body dispersion effects and vibrational free energies can be crucial for the description of relative stabilities, especially for highly polymorphic systems. The presented approach enables the calculation of reliable structures and thermodynamic stabilities for pharmaceutically relevant systems, contributing to a better understanding of complex polymorphic energy landscapes. Furthermore, many first-principles calculations are performed by using fully optimized structures and free energies obtained within the harmonic approximation, neglecting the thermal expansion of the studied molecular crystal and further anharmonic effects. Therefore, this thesis illustrates that the majority of the thermal expansion of molecular crystals can be captured with the used methods by applying the quasi-harmonic approximation. In addition, we estimate further anharmonic effects on the vibrational frequencies by utilizing Morse oscillators. [less ▲]

Detailed reference viewed: 153 (18 UL)
Full Text
Peer Reviewed
See detailHidden Beneath the Surface: Origin of the Observed Enantioselective Adsorption on PdGa(111)
Yakutovich, Aliaksandr V.; Hoja, Johannes UL; Passerone, Daniele et al

in Journal of the American Chemical Society (2018), 140(4), 1401-1408

Detailed reference viewed: 279 (4 UL)
Full Text
Peer Reviewed
See detailPowder diffraction and crystal structure prediction identify four new coumarin polymorphs
Shtukenberg, Alexander G.; Zhu, Qiang; Carter, Damien J. et al

in Chemical Science (2017)

Coumarin, a simple, commodity chemical isolated from beans in 1820, has, to date, only yielded one solid state structure. Here, we report a rich polymorphism of coumarin grown from the melt. Four new ... [more ▼]

Coumarin, a simple, commodity chemical isolated from beans in 1820, has, to date, only yielded one solid state structure. Here, we report a rich polymorphism of coumarin grown from the melt. Four new metastable forms were identified and their crystal structures were solved using a combination of computational crystal structure prediction algorithms and X-ray powder diffraction. With five crystal structures, coumarin has become one of the few rigid molecules showing extensive polymorphism at ambient conditions. We demonstrate the crucial role of advanced electronic structure calculations including many-body dispersion effects for accurate ranking of the stability of coumarin polymorphs and the need to account for anharmonic vibrational contributions to their free energy. As such, coumarin is a model system for studying weak intermolecular interactions, crystallization mechanisms, and kinetic effects. [less ▲]

Detailed reference viewed: 200 (3 UL)
Full Text
Peer Reviewed
See detailStrong Local-Field Enhancement of the Nonlinear Soft-Mode Response in a Molecular Crystal
Folpini, Giulia; Reimann, Klaus; Woerner, Michael et al

in Physical Review Letters (2017), 119

Detailed reference viewed: 156 (4 UL)
Full Text
Peer Reviewed
See detailFirst-principles modeling of molecular crystals: structures and stabilities, temperature and pressure
Hoja, Johannes UL; Reilly, Anthony M.; Tkatchenko, Alexandre UL

in Wiley Interdisciplinary Reviews: Computational Molecular Science (2016)

The understanding of the structure, stability, and response properties of molecular crystals at finite temperature and pressure is crucial for the field of crystal engineering and their application. For a ... [more ▼]

The understanding of the structure, stability, and response properties of molecular crystals at finite temperature and pressure is crucial for the field of crystal engineering and their application. For a long time, the field of crystal-structure prediction and modeling of molecular crystals has been dominated by classical mechanistic force-field methods. However, due to increasing computational power and the development of more sophisticated quantum-mechanical approximations, first-principles approaches based on density functional theory can now be applied to practically relevant molecular crystals. The broad transferability of first-principles methods is especially imperative for polymorphic molecular crystals. This review highlights the current status of modeling molecular crystals from first principles. We give an overview of current state-of-the-art approaches and discuss in detail the main challenges and necessary approximations. So far, the main focus in this field has been on calculating stabilities and structures without considering thermal contributions. We discuss techniques that allow one to include thermal effects at a first-principles level in the harmonic or quasi-harmonic approximation, and that are already applicable to realistic systems, or will be in the near future. Furthermore, this review also discusses how to calculate vibrational and elastic properties. Finally, we present a perspective on future uses of first-principles calculations for modeling molecular crystals and summarize the many remaining challenges in this field. [less ▲]

Detailed reference viewed: 225 (8 UL)
Full Text
Peer Reviewed
See detailReport on the sixth blind test of organic crystal structure prediction methods
Reilly, Anthony M.; Cooper, Richard I.; Adjiman, Claire S. et al

in Acta Crystallographica Section B (2016), 72(4), 439--459

The sixth blind test of organic crystal structure prediction (CSP) methods has been held, with five target systems: a small nearly rigid molecule, a polymorphic former drug candidate, a chloride salt ... [more ▼]

The sixth blind test of organic crystal structure prediction (CSP) methods has been held, with five target systems: a small nearly rigid molecule, a polymorphic former drug candidate, a chloride salt hydrate, a co-crystal and a bulky flexible molecule. This blind test has seen substantial growth in the number of participants, with the broad range of prediction methods giving a unique insight into the state of the art in the field. Significant progress has been seen in treating flexible molecules, usage of hierarchical approaches to ranking structures, the application of density-functional approximations, and the establishment of new workflows and `best practices' for performing CSP calculations. All of the targets, apart from a single potentially disordered Z$^\prime$ = 2 polymorph of the drug candidate, were predicted by at least one submission. Despite many remaining challenges, it is clear that CSP methods are becoming more applicable to a wider range of real systems, including salts, hydrates and larger flexible molecules. The results also highlight the potential for CSP calculations to complement and augment experimental studies of organic solid forms. [less ▲]

Detailed reference viewed: 204 (4 UL)