We combine a regularized variant of the strongly constrained and appropriately normed semilocal density functional [J. Sun, A. Ruzsinszky, and J. P. Perdew, Phys. Rev. Lett. 115, 036402 (2015)] with the latest generation semi-classical London dispersion correction. The resulting density functional approximation r2SCAN-D4 has the speed of generalized gradient approximations while approaching the accuracy of hybrid functionals for general chemical applications. We demonstrate its numerical robustness in real-life settings and benchmark molecular geometries, general main group and organo-metallic thermochemistry, and non-covalent interactions in supramolecular complexes and molecular crystals. Main group and transition metal bond lengths have errors of just 0.8%, which is competitive with hybrid functionals for main group molecules and outperforms them for transition metal complexes. The weighted mean absolute deviation (WTMAD2) on the large GMTKN55 database of chemical properties is exceptionally small at 7.5 kcal/mol. This also holds for metal organic reactions with an MAD of 3.3 kcal/mol. The versatile applicability to organic and metal-organic systems transfers to condensed systems, where lattice energies of molecular crystals are within the chemical accuracy (errors <1 kcal/mol).

TURBOMOLE is a collaborative, multi-national software development project aiming to provide highly efficient and stable computational tools for quantum chemical simulations of molecules, clusters, periodic systems, and solutions. The TURBOMOLE software suite is optimized for widely available, inexpensive, and resource-efficient hardware such as multi-core workstations and small computer clusters. TURBOMOLE specializes in electronic structure methods with outstanding accuracy–cost ratio, such as density functional theory including local hybrids and the random phase approximation (RPA), GW-Bethe–Salpeter methods, second-order Møller–Plesset theory, and explicitly correlated coupled-cluster methods. TURBOMOLE is based on Gaussian basis sets and has been pivotal for the development of many fast and low-scaling algorithms in the past three decades, such as integral-direct methods, fast multipole methods, the resolution-of-the-identity approximation, imaginary frequency integration, Laplace transform, and pair natural orbital methods. This review focuses on recent additions to TURBOMOLE’s functionality, including excited-state methods, RPA and Green’s function methods, relativistic approaches, high-order molecular properties, solvation effects, and periodic systems. A variety of illustrative applications along with accuracy and timing data are discussed. Moreover, available interfaces to users as well as other software are summarized. TURBOMOLE’s current licensing, distribution, and support model are discussed, and an overview of TURBOMOLE’s development workflow is provided. Challenges such as communication and outreach, software infrastructure, and funding are highlighted.

We present a new and entirely mechanistic COSMOperm method to predict passive membrane permeabilities for neutral compounds, as well as anions and cations. The COSMOperm approach is based on compound-specific free energy profiles within a membrane of interest from COSMO-RS (conductor-like screening model for realistic solvation) calculations. These are combined with membrane layer-specific diffusion coefficients, for example, in the water phase, the polar head groups, and the alkyl tails of biochemical phospholipid bilayers. COSMO-RS utilizes first-principle quantum chemical structures and physically sound intermolecular interactions (electrostatic, hydrogen bond, and van der Waals). For this reason, it is unbiased toward different application scenarios, such as in cosmetics and industrial chemical or pharmaceutical industries. A fully predictive calculation of passive permeation through phospholipid bilayer membranes results in a performance of r(2) = 0.92; rmsd = 0.90 log(10), units for neutral compounds and anions, as compared to gold standard black lipid membrane experiments. It will be demonstrated that new membrane types can be generated by the related COSMOplex method and directly used for permeability studies by COSMOperm.

We report the rigorous extension of COSMO-RS to a self-consistent prediction of the structure and the free energies of molecules in self-organizing inhomogeneous systems. This extends the application range to many new areas, as the prediction of micellar structure and critical micelle concentrations, finite loading effects in micelles and biomembranes, free energies and structure of liquid interfaces, micro-emulsions, and many more of similar problems, which often are of huge practical importance.

These abstracts were presented at the 2017 annual meeting of the UK In Vitro Toxicology Society (IVTS). The meeting was hosted at the Senate House in London, UK on November 23–24, 2017. The main session topics included hepatotoxicity; dermal and barrier toxicity; IVIVE, exposure and non-mammalian; cardiotoxicity; neurotoxicity; and genotoxicity.

Hartree–Fock theory is one of the most ancient methods of computational chemistry, but up to the present day quantum chemical calculations on Hartree–Fock level or with hybrid density functional theory can be excessively time consuming. We compare three currently available techniques to reduce the computational demands of such calculations in terms of timing and accuracy.

The partition coefficient of chemicals from water to phospholipid membrane, K-lipw, is of central importance for various fields. For neutral organic molecules, log K-lipw correlates with the log of bulk solvent-water partition coefficients such as the octanol-water partition coefficient. However, this is not the case for charged compounds, for which a mechanistic modeling approach is highly necessary. In this work, we extend the model COSMOmic, which adapts the COSMO-RS theory for anisotropic phases and has been shown to reliably predict K-lipw for neutral compounds, to the use of ionic compounds. To make the COSMOmic model applicable for ionic solutes, we implemented the internal membrane dipole potential in COSMOmic. We empirically optimized the potential with experimental K-lipw data of 161 neutral and 75 ionic compounds, yielding potential shapes that agree well with experimentally determined potentials from the literature. This model refinement has no negative effect on the prediction accuracy of neutral compounds (root-mean-square error, RMSE = 0.62 log units), while it highly improves the prediction of ions (RMSE = 0.70 log units). The refined COSMOmic is, to our knowledge, the first mechanistic model that predicts K-lipw of both ionic and neutral species with accuracies better than 1 log unit.

We give a brief exposition of the fundamental approximations of ab initio calcu- lations, the SCF, DFT and MP2 methods for calculating molecular wavefunctions and energies are introduced. The Resolution of Identity (RI) approach is described with a view to the treatment of large molecules (100 atoms and more). Scaling behavior of the various computational methods is compared; here, aluminium clus- ters represent a demanding application. The utility of analytical energy gradients is shown, in particular using the example of a theoretical study of the structural isomers of sulfur-bridged copper clusters. A strategy to compute electronic excitation energies for large molecules is sketched and applications to fullerenes and cadmium-selenide nanoclusters are presented. Developments in scientific computing hardware are considered, with emphasis on the emergence of PC’s. The oppor- tunities and difficulties inherent in the parallelization of quantum chemical code are also discussed, and the performance of parallel TURBOMOLE is presented.

We present thermocalc , a Perl module to perform the automated calculation of atomization energies and heats of formation for lists of molecules. The methods used are based on density functional theory and second‐order perturbation theory to ensure that data sets of medium sized to large molecules can be run at reasonable throughput rates. The quantum chemical calculations are performed using the program package TURBOMOLE in a three‐step protocol. In a first step, a pre‐optimization of the structure and a zero‐point energy calculation are performed. As second step, a geometry optimization is being carried out, and the last step is a single point energy calculation. The level of theory used in the different steps can be modified by the user to allow for customized protocols. The performance of example protocols is investigated on different test sets of molecules. In the course of this work, a simple, but efficient one‐parameter correction term based on the shared electron numbers has been developed, which reduces the error of calculated heats of formation significantly. © 2012 Wiley Periodicals, Inc.

We herein present the graphical user interface (GUI) TmoleX for the quantum chemical program package TURBOMOLE. TmoleX allows users to execute the complete workflow of a quantum chemical investigation from the initial building of a structure to the visualization of the results in a user friendly graphical front end. The purpose of TmoleX is to make TURBOMOLE easy to use and to provide a high degree of flexibility. Hence, it should be a valuable tool for most users from beginners to experts. The program is developed in Java and runs on Linux, Windows, and Mac platforms. It can be used to run calculations on local desktops as well as on remote computers. © 2010 Wiley Periodicals, Inc. J Comput Chem 2010

A new approach for the modeling of molecules in micellar systems and especially in biomembranes, COSMOmic, is presented, and its performance is validated on the example of the partitioning of molecules between water and biological membranes. Starting from quantum chemical calculations of the surfactant, solvent, and solute molecules, and being based on the COSMO-RS method for fluid-phase thermodynamic properties, COSMOmic is essentially free of additional adjustable parameters. The inclusion of an elastic energy correction into the COSMOmic model did not turn out to yield any significant improvement. The novel COSMOmic method allows for the efficient prediction of the distribution of molecules in micellar systems.

Pure liquid niobium chloride and solid and liquid NbCl5-alkali chloride solutions were for the first time studied by Nb-93 NMR. Chemical shift (delta) and line width (Deltav(1/2)) measurements were made by using a laboratory made probe head for experiments at elevated temperatures up to 650degreesC. In the case of NbCl5-(LiCl/KCl)(eut), where the salt mixture was not opaque, also Raman spectra could be recorded. For pure liquid NbCl5 the monomer-dimer equilibrium could be investigated. In the temperature range 200degreesC to ca. 500degreesC from the temperature dependence of both delta and Deltav(1/2) the equilibrium constant and the standard entropy and enthalpy for this reaction have been obtained. Binary NbCl5-CsCl and NbCl5-NaCl salt melts and solutions of NbCl5 in solid and liquid eutectic mixtures were investigated by Nb-93 NMR. For some mixtures where the phase behaviour was only partially known, additional differential thermoanalysis (DTA) measurements of the phase diagrams have been performed. By Nb-93 NMR a distinctly different behaviour of CsCl and NaCl containing melts is observed, where the the CsCl melts show relative broad resonance lines and a large negative chemical shift, whereas the NaCl melts reveal typically narrow lines and positive shifts. The broad lines are discussed with respect to the self-reduction reaction Nb5+ --> Nb4+. In the high temperature solid phases of both NaCl and CsCl containing mixtures unusually narrow lines are explained by a fast ionic hopping process in these materials. The stability of oxy complexes in different salt matrices is also discussed. Finally, the observed temperature dependence of the Nb-93 chemical shift (ca. 0.1 ppm K-1) in different salt mixtures is found to be in qualitative agreement with a theoretical estimate, which considers the Nb-Cl distance variation with temperature.

Density functional theory (DFT) calculations have been performed on the nitrogenase cofactor, FeMoco. Issues that have been addressed concern the nature of M-M interactions and the identity and origin of the central light atom, revealed in a recent crystallographic study of the FeMo protein of nitrogenase (Einsle, O.; et al. Science 2002, 297, 871). Introduction of Se in place of the S atoms in the cofactor and energy minimization results in an optimized structure very similar to that in the native enzyme. The nearly identical, short, lengths of the Fe-Fe distances in the Se and S analogues are interpreted in terms of M-M weak bonding interactions. DFT calculations with O or N as the central atoms in the FeMoco marginally support the assignment of the central atom as N rather than O. The assumption was made that the central atom is the N atom, and steps of a catalytic cycle were calculated starting with either of two possible states for the cofactor and maintaining the same charge throughout (by addition of equal numbers of H(+) and e(-)) between steps. The states were [(Cl)Fe(II)(6)Fe(III)Mo(IV)S(9)(H(+))(3)N(3-)(Gl)(Im)](2-), [I-N-3H](2-), and [(Cl)Fe(II)(4)Fe(III)(3)Mo(IV)S(9)(H(+))(3)N(3-)(Gl)(Im)], [I-N-3H](0) (Gl = deprotonated glycol; Im = imidazole). These are the triply protonated ENDOR/ESEEM [I-N](5-) and Mössbauer [I-N](3-) models, respectively. The proposed mechanism explores the possibilities that (a) redox-induced distortions facilitate insertion of N(2) and derivative substrates into the Fe(6) central unit of the cofactor, (b) the central atom in the cofactor is an exchangeable nitrogen, and (c) the individual steps are related by H(+)/e(-) additions (and reduction of substrate) or aquation/dehydration (and distortion of the Fe(6) center). The Delta E's associated with the individual steps of the proposed mechanism are small and either positive or negative. The largest positive Delta E is +121 kJ/mol. The largest negative Delta E of -333 kJ/mol is for the FeMoco with a N(3-) in the center (the isolated form) and an intermediate in the proposed mechanism.

Reaction of the mono-deprotonated derivative of [{CP(CO)(2)Mo}(2)(mu-PH2)(mu-H)] (1) leads to the novel complex [{CP(CO)(2)Mo}(2)(mu-H){mu(3)-P(H)Au(PPh3)}] (2). In contrast the reaction of the analogous Cr derivative [{CP(CO)(2)Cr}(2)(mu-PH2)(mu-H)] (1a) leads under identical conditions to a planar Au3P3 cluster [{CpCr(CO)(2)}(6)(P3Au3)] (3). Both complexes were completely structurally and spectroscopically characterised. Density functional calculations have shown that 3 is characterised by P-Cr-Au multicentre and Cr-P multiple bonding. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Forming a phosphorus envelope: The first structurally characterized cyclooligophosphanide ion [cyclo-(P5 tBu4 )]- to be obtained by a targeted synthesis reacts with [NiCl2 (PEt3 )2 ] by loss of a tBu group to give (η2 -3,4,5-tri-tert-butylcyclopentaphosphene)bis(triethylphosphane)nickel(0) (1). The previously unknown cyclopentaphosphene ring in 1 has an envelope conformation in solution and in the solid state, and the tBu groups adopt an all-trans configuration.

Das erste gezielt herstellbare, strukturell charakterisierte Cyclooligophosphanid-Anion [cyclo-(P5tBu4)]− reagiert mit [NiCl2(PEt3)2] unter Verlust einer tBu-Gruppe zu (η2-3,4,5-Tri-tert-butylcyclopentaphosphen)bis(triethylphosphan)nickel(0) 1. Der bislang unbekannte Cyclopentaphosphen-Ring in 1 liegt sowohl im Festkörper als auch in Lösung in einer Envelope-Konformation vor, und die tBu-Gruppen sind all-trans-konfiguriert.

An intermediate on the pathway from AlI species to aluminum metal: This is one way to view the [Al14{N(SiMe3)2}6I6]2− cluster (structure shown) formed from the reaction of an aluminum(I) iodide solution with LiN(SiMe3)2. With the help of density functional calculations it was confirmed that the observed metalloid structure is more favorable for the Al14 cluster than a polyhedral structure that follows Wade's rules.

Als ein Intermediat auf dem Weg von AlI-Spezies zum Aluminiummetall kann der bei der Umsetzung von AlI-Iodid-Lösung mit LiN(SiMe3)2 entstehende [Al14{N(SiMe3)2}6I6]2−-Cluster (Struktur siehe Bild) angesehen werden. Mit Hilfe von Dichtefunktionaltheorie-Rechnungen wird bestätigt, dass die beobachtete metalloide Struktur für den Al14-Cluster günstiger ist als eine polyedrische Struktur mit Wade-Bindungsverhältnissen.