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Using water as a monomer in polymerization reactions presents a unique and exquisite strategy towards more sustainable chemistry. Herein, the feasibility thereof is demonstrated by the introduction of the oxa-Michael polyaddition of water and divinyl sulfone. Upon nucleophilic or base catalysis, the corresponding aliphatic polyethersulfone is obtained in an interfacial polymerization at room temperature in high yield (>97%) within an hour. The polyethersulfone is characterized by relatively high molar mass averages and a dispersity around 2.5. The polymer was tested as a solid polymer electrolyte with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as the salt. Free-standing amorphous membranes were prepared by a melt process in a solvent-free manner. The polymer electrolyte containing 15 wt% LiTFSI featured an oxidative stability of up to 5.5 V vs. Li/Li+ at 45 °C and a conductivity of 1.45 × 10−8 S cm−1 at room temperature.

Electron-rich triarylphosphines, namely 4-(methoxyphenyl)diphenylphosphine (MMTPP) and tris(4-trimethoxyphenyl)phosphine (TMTPP), outperform commonly used triphenylphosphine (TPP) in catalyzing oxa-Michael additions. A matrix consisting of three differently strong Michael acceptors and four alcohols of varying acidity was used to assess the activity of the three catalysts. All test reactions were performed with 1 mol % catalyst loading, under solvent-free conditions and at room temperature. The results reveal a decisive superiority of TMTPP for converting poor and intermediate Michael acceptors such as acrylamide and acrylonitrile and for converting less acidic alcohols like isopropanol. With stronger Michael acceptors and more acidic alcohols, the impact of the more electron-rich catalysts is less pronounced. The experimental activity trend was rationalized by calculating the Michael acceptor affinities of all phosphine–Michael acceptor combinations. Besides this parameter, the acidity of the alcohol has a strong impact on the reaction speed. The oxidation stability of the phosphines was also evaluated and the most electron-rich TMTPP was found to be only slightly more sensitive to oxidation than TPP. Finally, the catalysts were employed in the oxa-Michael polymerization of 2-hydroxyethyl acrylate. With TMTPP polymers characterized by number average molar masses of about 1200 g/mol at room temperature are accessible. Polymerizations carried out at 80 °C resulted in macromolecules containing a considerable share of Rauhut–Currier-type repeat units and consequently lower molar masses were obtained.

Several amines with three bulky alkyl groups at the nitrogen atom, which exceed the steric crowding of triisopropylamine significantly, were synthesized, mainly by treating N‐chlorodialkylamines with Grignard reagents. In six cases, namely tert‐butyldiisopropylamine, 1‐adamantyl‐tert‐butylisopropylamine, di‐1‐adamantylamines with an additional N‐cyclohexyl or N‐exo‐2‐norbonyl substituent, as well as 2,2,6,6‐tetramethylpiperidine derivatives with N‐cyclohexyl or N‐neopentyl groups, appropriate single crystals were generated that enabled X‐ray diffraction studies and analysis of the molecular structures. The four noncyclic amines adopt triskele‐like conformations, and the sum of the three C−N−C angles is always in the range of 351.1° to 352.4°. Consequently, these amines proved to be structurally significantly flatter than trialkylamines without steric congestion, which is also signalized by the smaller heights of the NC3 pyramids (0.241–0.259 Å). There is no clear correlation between the heights of these pyramids and the degree of the steric crowding in the new amines, presumably because steric repulsion is partly compensated by dispersion interaction. In the cases of the two heterocyclic amines, the steric stress is smaller, and the molecular structures include quite different conformations. Quantum chemical calculations led to precise gas‐phase structures of the sterically overcrowded trialkylamines exhibiting heights of the NC3 pyramids and preferred molecular conformers which are similar to those resulting from the X‐ray studies., Chemistry - A European Journal, 27 (11), ISSN:0947-6539, ISSN:1521-3765

3,3-Bis(2,4,6-triisopropylphenyl)-1,1-binaphthyl-2,2-diyl hydrogenphosphate (TRIP) catalyzes the asymmetric allylation of aldehydes with organozinc compounds, leading to highly valuable structural motifs, like precursors to lignan natural products. Our previously reported mechanistic proposal relies on two reaction intermediates and requires further investigation to really understand the mode of action and the origins of stereoselectivity. Detailed ab initio calculations, supported by experimental data, render a substantially different mode of action to the allyl boronate congener. Instead of a Brønsted acid-based catalytic activation, the chiral phosphate acts as a counterion for the Lewis acidic zinc ion, which provides the activation of the aldehyde.

Using water as monomer in polymerization reactions presents a unique and exquisite strategy towards more sustainable chemistry. Herein, the feasibility thereof is demonstrated by the introduction of the oxa-Michael polyaddition of water and divinyl sulfone. Upon nucleophilic or base catalysis, the corresponding aliphatic polyethersulfone is obtained in an interfacial polymerization at room temperature in high yield (> 97%) within an hour. The polyethersulfone is characterized by relatively high molar mass averages and a dispersity around 2.5. The polymer was tested as a solid polymer electrolyte with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as salt. Free standing amorphous membranes were prepared by a melt process in a solvent free manner. The polymer electrolyte containing 15 wt.% LiTFSI featured an oxidation stability of up to 5.5 V vs. Li/Li+ at 45 °C and a conductivity of 1.45 × 10-8 S/cm at room temperature.

New sets of empirical D3 and many-body dispersion parameters to be used with the density-functional tight-binding method have been derived. These sets are aimed at a better description of cell volumes of molecular crystals. The validation of these parameters against the extended data set of molecular crystals resulted in better geometric and slightly worse energetic characteristics. A comparison between the empirical D3 and many-body dispersion schemes in describing the properties of molecular crystals yielded almost identical results. The proposed parameters should serve as a useful tool for further investigations of molecular crystal properties.

We present revised reference values for cell volumes and lattice energies for the widely used X23 benchmark set of molecular crystals by including the effect of thermal expansion. For this purpose, thermally-expanded structures were calculated via the quasi-harmonic approximation utilizing three dispersion-inclusive density-functional approximations. Experimental unit-cell volumes were back-corrected for thermal and zero-point energy effects, allowing now a direct comparison with lattice relaxations based on electronic energies. For the derivation of reference lattice energies, we utilized harmonic vibrational contributions averaged over four density-functional approximations. In addition, the new reference values also take the change in electronic and vibrational energy due to thermal expansion into account. This is accomplished by either utilizing experimentally determined cell volumes and heat capacities, or by relying on the quasi-harmonic approximation. The new X23b reference values obtained this way will enable a more accurate benchmark for the performance of computational methods for molecular crystals.

The terminal zinc hydride complex [Tntm]ZnH (2; Tntm=tris(6-tert-butyl-3-thiopyridazinyl)methanide) is an efficient hydrosilylation catalyst of CO2 at room temperature without the need of Lewis acidic additives. The inherent electrophilicity of the system leads to selective formation of the monosilylated product (MeO)3 SiO2 CH (at room temperature with a TOF of 22.2 h-1 and at 45 °C with a TOF of 66.7 h-1 ). In absence of silanes, the intermediate formate complex [Tntm]Zn(O2 CH) (3) is quantitatively formed within 5 min. All complexes were fully characterized by 1 H and 13 C NMR spectroscopy and single-crystal X-ray diffraction analyses. Density functional theory (DFT) calculations reveal a high positive charge on zinc and the increased preference of the ligand to adopt a κ3 -coordination mode.

The Sr-free mixed ionic electronic conducting perovskites La0.8Ca0.2FeO3-δ (LCF82) and Pr0.8Ca0.2FeO3-δ (PCF82) were synthesized via a glycine-nitrate process. Crystal structure, phase purity, and lattice constants were determined by XRD and Rietveld analysis. The oxygen exchange kinetics and the electronic conductivity were obtained from in-situ dc-conductivity relaxation experiments at 600–800 °C and 1×10−3≤pO2/bar≤0.1. Both LCF82 and PCF82 show exceptionally fast chemical surface exchange coefficients and chemical diffusion coefficients of oxygen. The oxygen nonstochiometry of LCF82 and PCF82 was determined by precision thermogravimetry. A point defect model was used to calculate the thermodynamic factors of oxygen and to estimate self-diffusion coefficients and ionic conductivities. Density Functional Theory (DFT) calculations on the crystal structure, oxygen vacancy formation as well as oxygen migration energies are in excellent agreement with the experimental values. Due to their favourable properties both LCF82 and PCF82 are of interest for applications in solid oxide fuel cell cathodes, solid oxide electrolyser cell anodes, oxygen separation membranes, catalysts, or electrochemical sensors.

We report an alternative quantum mechanical:quantum mechanical (QM:QM) method to the currently used periodic density functional calculations including dispersion and investigate its performance with respect to main structural and energetic properties of the X23 set of molecular crystals. By setting the goal of reproducing reference periodic BLYP+D3 values and by embedding BLYP+D3 into DFTB, we obtain results similar to those of periodic BLYP+D3-typically within 1-2% in lattice energies and ∼0.4% in cell volumes. The accuracy of this QM:QM method in comparison to DFTB+D and DFT+D for the X23 set of molecular crystals is discussed.

The ligand tris(6-tert-butyl-3-thiopyridazinyl)methane ([Tntm]H) was synthesized by the reaction of 6-tert-butyl-3-thiopyridazine with bromoform and reacted with zinc bis(trimethylsilylamide) (Zn(N{SiMe3}2)2) to form [Tntm]Zn(N{SiMe3}2) (1). This complex further reacts with protic and acidic substrates, generating the zinc thiolate complex [Tntm]Zn(StBu) (2) and zinc benzoate complex [Tntm]Zn(O2C-Me2C6H3) (3a). In all compounds [Tntm] was found to have tridentate coordination to the metal center in a κ3-C,N,N fashion, as established by single-crystal X-ray diffraction analyses. In solution, rapid dynamic κ3/κ4 equilibrium occurs at room temperature, while 1H NMR spectroscopy at −30 °C confirms the asymmetric solid-state structure. Furthermore, complex 3a shows a rearrangement reaction in solution where the ligand isomerizes to give a κ4-C,N,N,S (3b) and a κ4-C,N,S,S isomer (3c), respectively. Density functional theory (DFT) calculations reveal 3b and 3c to be 13.7 and 15.6 kJ/mol more stable in methylene ...

A hybrid method is introduced and applied that combines second-order Moller–Plesset perturbation theory (MP2) for cluster models with density functional theory for periodic models to obtain structures and energetics for molecular crystals of the alkane species, notably propane. Calculated lattice energies elucidate the fact that propane has the lowest melting temperature of all organic compounds. The hybrid method provides an alternative to currently existing methods, which use either periodic MP2 for the determination of periodic crystals or periodic DFT+D. We also compare the hybrid method to a number of modern density functionals which are commonly used for the computation of molecular crystals. Depending on the functional used, we get a large range of lattice energies. From our QM:QM results, we can deduce that the achievements of DFT+D for computing molecular crystals largely relies on error cancellation effects between the functional and its dispersion coefficients.

Adsorption energies of various nitrogen-containing compounds (specifically, 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4-dinitroanisole (DNAn), and 3-nitro-1,2,4-triazole-5-one (NTO)) on the hydroxylated (001) and (100) α-quartz surfaces are computed. Different density functionals are utilized and both periodic as well as cluster approaches are applied. From the adsorption energies, partition coefficients on the considered α-quartz surfaces are derived. While TNT and DNT are preferably adsorbed on the (001) surface of α-quartz, NTO is rather located on both α-quartz surfaces.

Symmetry Adapted Perturbation Theory (SAPT) has become an important tool when predicting and analyzing intermolecular interactions. Unfortunately, DFT-SAPT, which uses Density Functional Theory (DFT) for the underlying monomers, has some arbitrariness concerning the exchange-correlation potential and the exchange-correlation kernel involved. By using ab initio Brueckner Doubles densities and constructing Kohn-Sham orbitals via the Zhao-Morrison-Parr (ZMP) method, we are able to lift the dependence of DFT-SAPT on DFT exchange-correlation potential models in first order. This way, we can compute the monomers at the Coupled-Cluster level of theory and utilize SAPT for the intermolecular interaction energy. The resulting ZMP-SAPT approach is tested for small dimer systems involving rare gas atoms, cations, and anions and shown to compare well with the Tang-Toennies model and coupled cluster results., 23 pages, 5 figures

In this work, we study the adsorption of CO from low to high coverage at a defect-free NaCl(100) surface by means of cluster and periodic models, using highly accurate wave function-based QM:QM embedding as well as density functional theory. At low coverages, the most accurate methods predict a zero-point-corrected adsorption energy of around 13 kJ/mol, and the CO molecules are found to be oriented perpendicular to the surface. At higher coverages, lower-energy phases with nonparallel/upright, tilted orientations emerge. Besides the well-known p(2 × 1)/antiparallel phase (T/A), we find other tilted phases (tilted/irregular, T/I; tilted/spiral, T/S) as local minima. Vibrational frequencies for CO adsorbed on NaCl(100) and Davydov splittings of the C–O stretch vibration are also determined. The IR spectra are characteristic fingerprints for the relative orientation of CO molecules and may therefore be used as sensitive probes to distinguish parallel/upright from various tilted adsorption phases.

The reaction mechanism for the rapid formation of a triplet oxygen atom, O((3)P), from a pair of triplet-state hydroxyl radicals in liquid water is explored utilizing extensive Car-Parrinello MD simulations and advanced visualization techniques. The local solvation structures, the evolution of atomic charges, atomic separations, spin densities, electron localization functions, and frontier molecular orbitals, as well as free energy profiles, evidence that the reaction proceeds through a hybrid (hydrogen atom transfer and electron-proton transfer) and hemibond-assisted reaction mechanism. A benchmarking study utilizing high-level ab initio calculations to examine the interactions of a hydroxyl radical pair in the gas phase and the influence of a hemibonded water is also provided. The results presented here should serve as a foundation for further experimental and theoretical studies aimed at better understanding the role and potential applications of the triplet oxygen atom as a potent reactive oxygen species.

The interactions of H2, CO, CO2, and H2O with the undercoordinated metal centers of the trimetallic oxo-centered M3(III)(μ3-O)(X) (COO)6 moiety are studied by means of wave function and density functional theory. This trimetallic oxo-centered cluster is a common building unit in several metal-organic frameworks (MOFs) such as MIL-100, MIL-101, and MIL-127 (also referred to as soc-MOF). A combinatorial computational screening is performed for a large variety of trimetallic oxo-centered units M3(III)O (M = Al(3+), Sc(3+), V(3+), Cr(3+), Fe(3+), Ga(3+), Rh(3+), In(3+), Ir(3+)) interacting with H2O, H2, CO, and CO2. The screening addresses interaction energies, adsorption enthalpies, and vibrational properties. The results show that the Rh and Ir analogues are very promising materials for gas storage and separations.

The terminal zinc hydride complex [Tntm]ZnH (2; Tntm=tris(6-tert-butyl-3-thiopyridazinyl)methanide) is an efficient hydrosilylation catalyst of CO

We introduce and employ two QM:QM schemes (a quantum mechanical method embedded into another quantum mechanical method) and report their performance for the X23 set of molecular crystals. We furthermore present the theory to calculate the stress tensors necessary for the computation of optimized cell volumes of molecular crystals and compare all results to those obtained with various density functionals and more approximate methods. Our QM:QM calculations with PBE0:PBE+D3, PBE0:PBE+MBD, and B3LYP:BLYP+D3 yield at a reduced computational cost lattice energy errors close to the ones of the parent hybrid density functional method, whereas for cell volumes, the errors of the QM:QM scheme methods are in between the GGA and hybrid functionals., Comment: Revised Manuscript accepted in "The Journal of Chemical Physics" (AIP)

Calculations at various levels of theory with different methods and respective evaluations confirm that the twist conformation (C2) is preferred for tetrahydrothiophene (THT) in the gas phase. In the crystalline phase, achieved by a laser assisted crystallization device, THT has C1 symmetry (slightly distorted C2 symmetry) in the chiral space group P212121. This is obviously a packing effect caused by the nonsymmetrical arrangement of neighboring molecules. The distortion from C2 symmetry costs very little energy as confirmed by computational methods in the gas phase. Only one enantiomer of the chiral THT is found in the cell which requires spontaneous crystallization, which results in a racemic mixture of crystals, or a racemization occurs prior to/during nucleation or in the “embryonic” state. The racemization happens by a mechanism that can be described as a partial pseudo rotation within a five-membered mono-heterocycle with a C2–CS–C2′ transition (C2 and C2′ are enantiomers) maintaining the heteroato...

As hydrogen-bonded systems are of utmost importance in especially biological and chemical systems, a new set of highly accurate reference dissociation energies, denoted HB49, is devised. For the molecules in this set, the basis set convergence of post-Hartree–Fock methods, including F12 methods, is investigated. Using combined Moller–Plesset perturbation theory (MP2) and CCSD(T) approaches for energies and MP2 and QCISD(T) for gradients, we achieve CCSD(T) accuracy, which has been determined before to yield an accuracy of 0.2 kJ/mol for a subset of HB49. Both conventional extrapolation techniques and F12 techniques are competitive with each other. By using MP2+ΔCCSD(T), a rather fast basis set convergence is obtained when both basis sets are carefully chosen.

A cluster approach extended to the ONIOM methodology has been applied using several density functionals and Moller–Plesset perturbation theory (MP2) to simulate the adsorption of selected nitrogen-containing compounds [NCCs, 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), 2,4-dinitroanisole (DNAN), and 3-nitro-1,2,4-triazole-5-one (NTO)] on the hydroxyated (100) surface of α-quartz. The structural properties were calculated using the M06-2X functional and 6-31G(d,p) basis set. The M06-2X-D3, PBE-D3, and MP2 methods were used to calculate the adsorption energies. Results have been compared with the data from other studies of adsorption of compounds of similar nature on silica. Effect of deformation of the silica surface and adsorbates on the binding energy values was also studied. The atoms in molecules (AIM) analysis was employed to characterize the adsorbate–adsorbent binding and to calculate the bond energies. The silica surface shows different sorption affinity toward the chemicals considered de...

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?? = 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. Fil: Reilly, Anthony M.. Cambridge Crystallographic Data Centre; Fil: Cooper, Richard I.. Chemistry Research Laboratory; Fil: Adjiman, Claire S.. Imperial College London; Reino Unido Fil: Bhattacharya, Saswata. Fritz Haber Institute Of The Max Planck Society; Fil: Boese, A. Daniel. Karl-franzens-universitat Graz; Austria Fil: Brandenburg, Jan Gerit. Colegio Universitario de Londres; Reino Unido. Universitat Bonn; Alemania Fil: Bygrave, Peter J.. University of Southampton; Reino Unido Fil: Bylsma, Rita. Radboud Universiteit Nijmegen; Países Bajos Fil: Campbell, Josh E.. University of Southampton; Reino Unido Fil: Car, Roberto. University of Princeton; Estados Unidos Fil: Case, David H.. University of Southampton; Reino Unido Fil: Chadha, Renu. University Institute Of Pharmaceutical Sciences India; India Fil: Cole, Jason C.. Cambridge Crystallographic Data Centre; Fil: Cosburn, Katherine. University of Tulane; Estados Unidos. University of Toronto; Canadá Fil: Cuppen, Herma M.. Radboud Universiteit Nijmegen; Países Bajos Fil: Curtis, Farren. University of Tulane; Estados Unidos. University of Carnegie Mellon; Estados Unidos Fil: Day, Graeme M.. University of Southampton; Reino Unido Fil: DiStasio, Robert A.. University of Princeton; Estados Unidos. Cornell University; Estados Unidos Fil: Dzyabchenko, Alexander. Karpov Institute Of Physical Chemistry; Fil: Van Eijck, Bouke P.. University of Utrecht; Países Bajos. Utrecht University; Países Bajos Fil: Elking, Dennis M.. Openeye Scientific Software, Inc; Fil: Van Den Ende, Joost A.. Radboud Universiteit Nijmegen; Países Bajos Fil: Facelli, Julio C.. University of Utah; Estados Unidos Fil: Ferraro, Marta B.. Universidad de Buenos Aires; Argentina Fil: Fusti-Molnar, Laszlo. Openeye Scientific Software, Inc; Fil: Gatsiou, Christina-Anna. Imperial College London; Reino Unido Fil: Gee, Thomas S.. University of Southampton; Reino Unido Fil: De Gelder, René. Radboud Universiteit Nijmegen; Países Bajos Fil: Ghiringhelli, Luca M.. Fritz Haber Institute Of The Max Planck Society; Fil: Goto, Hitoshi. Toyohashi University Of Technology; Fil: Grimme, Stefan. Universitat Bonn; Alemania Fil: Guo, Rui. Colegio Universitario de Londres; Reino Unido Fil: Hofmann, Detlef W. M.. Flexcryst; . Polaris; Fil: Hoja, Johannes. Fritz Haber Institute Of The Max Planck Society; Fil: Hylton, Rebecca K.. Colegio Universitario de Londres; Reino Unido Fil: Iuzzolino, Luca. Colegio Universitario de Londres; Reino Unido Fil: Jankiewicz, Wojciech. University Of Silesia In Katowice; Fil: De Jong, Daniël T.. Radboud Universiteit Nijmegen; Países Bajos Fil: Kendrick, John. University Of Bradford; Fil: De Klerk, Niek J. J.. Radboud Universiteit Nijmegen; Países Bajos Fil: Ko, Hsin-Yu. University of Princeton; Estados Unidos Fil: Kuleshova, Liudmila N.. Flexcryst; Fil: Li, Xiayue. University of Tulane; Estados Unidos. Argonne National Laboratory; Estados Unidos Fil: Lohani, Sanjaya. University of Tulane; Estados Unidos Fil: Leusen, Frank J. J.. University Of Bradford; Fil: Lund, Albert M.. University of Utah; Estados Unidos. Openeye Scientific Software, Inc; Fil: Lv, Jian. Jilin University; China Fil: Ma, Yanming. Jilin University; China Fil: Marom, Noa. University of Carnegie Mellon; Estados Unidos. University of Tulane; Estados Unidos Fil: Masunov, Artëm E.. University Of Central Florida; . National Research Nuclear University Mephi; Fil: McCabe, Patrick. Cambridge Crystallographic Data Centre; Fil: McMahon, David P.. University of Southampton; Reino Unido Fil: Meekes, Hugo. Radboud Universiteit Nijmegen; Países Bajos Fil: Metz, Michael P.. University Of Delaware; Fil: Misquitta, Alston J.. Queen Mary, University Of London; Fil: Mohamed, Sharmarke. Khalifa University Of Science And Technology; Fil: Monserrat, Bartomeu. Rutgers, The State University Of New Jersey; . University of Cambridge; Estados Unidos Fil: Needs, Richard J.. University of Cambridge; Estados Unidos Fil: Neumann, Marcus A.. No especifica; Fil: Nyman, Jonas. University of Southampton; Reino Unido Fil: Obata, Shigeaki. Toyohashi University Of Technology; Fil: Oberhofer, Harald. Universitat Technical Zu Munich; Alemania Fil: Oganov, Artem R.. Northwestern Polytechnical University; China. Skolkovo Institute Of Science And Technology; . Moscow Institute Of Physics And Technology; . Stony Brook University; Fil: Orendt, Anita M.. University of Utah; Estados Unidos Fil: Pagola, Gabriel Ignacio. Universidad de Buenos Aires; Argentina Fil: Pantelides, Constantinos C.. Imperial College London; Reino Unido Fil: Pickard, Chris J.. University of Cambridge; Estados Unidos. Colegio Universitario de Londres; Reino Unido Fil: Podeszwa, Rafal. University Of Silesia In Katowice; Fil: Price, Louise S.. Colegio Universitario de Londres; Reino Unido Fil: Price, Sarah L.. Colegio Universitario de Londres; Reino Unido Fil: Pulido, Angeles. University of Southampton; Reino Unido Fil: Read, Murray G.. Cambridge Crystallographic Data Centre; Fil: Reuter, Karsten. Universitat Technical Zu Munich; Alemania Fil: Schneider, Elia. University of New York; Estados Unidos Fil: Schober, Christoph. Universitat Technical Zu Munich; Alemania Fil: Shields, Gregory P.. Cambridge Crystallographic Data Centre; Fil: Singh, Pawanpreet. University Institute Of Pharmaceutical Sciences India; India Fil: Sugden, Isaac J.. Imperial College London; Reino Unido Fil: Szalewicz, Krzysztof. University Of Delaware; Fil: Taylor, Christopher R.. University of Southampton; Reino Unido Fil: Tkatchenko, Alexandre. University Of Luxembourg; . Fritz Haber Institute Of The Max Planck Society; Fil: Tuckerman, Mark E.. University of New York; Estados Unidos. New York University Shanghai; China. Courant Institute Of Mathematical Sciences; Fil: Vacarro, Francesca. University of Tulane; Estados Unidos. Loyola University New Orleans; Fil: Vasileiadis, Manolis. Imperial College London; Reino Unido Fil: Vazquez-Mayagoitia, Alvaro. Argonne National Laboratory; Estados Unidos Fil: Vogt, Leslie. University of New York; Estados Unidos Fil: Wang, Yanchao. Jilin University; China Fil: Watson, Rona E.. Colegio Universitario de Londres; Reino Unido Fil: De Wijs, Gilles A.. Radboud Universiteit Nijmegen; Países Bajos Fil: Yang, Jack. University of Southampton; Reino Unido Fil: Zhu, Qiang. Stony Brook University; Fil: Groom, Colin R.. Cambridge Crystallographic Data Centre

A hybrid method is applied that combines second order Moller-Plesset perturbation theory (MP2) for cluster models with density functional theory for periodic (slab) models to obtain structures and energies for methane and ethane molecules adsorbed on the MgO(001) surface. Single point calculations are performed to estimate the effect of increasing the cluster size on the MP2 energies and to evaluate the difference between coupled cluster (CCSD(T)) and MP2 energies. The final estimates of the adsorption energies are 12.9 ± 1.3 and 18.9 ± 1.8 kJ/mol for CH4 and C2 H6 , respectively. © 2016 Wiley Periodicals, Inc.

Density functional theory is used to study the redispersion of clusters of one to six Au atoms by 1,3,5-tris(phenylthio)benzene (TPB) on the Au(111) surface. The adopted computational scheme PBE+dispersion is first assessed by comparison with available experimental (cohesive properties of gold) and CCSD(T) results (gas-phase complexes of H 2S and 1,3,5-tristhiobenzene with gold atoms). Comparison is also made with B3LYP+dispersion. The stability of complexes between TPB and gold adatoms on the Au(111) surface is investigated showing that TPB is able to bind up to six isolated gold adatoms, to extract an adatom from a gold island, and to break apart small gold clusters on the surface. © 2011 American Chemical Society.

To assess the accuracy of post-Hartree-Fock methods like CCSD(T), MP3, MP2.5, MP2, SCS-MP2, SOS-MP2, and DFT-SAPT, we evaluated several effects going beyond valence-correlated CCSD(T). For 16 small hydrogen bonded systems, CCSD(T) achieves an RMS error of 0.17 kJ/mol in the dissociation energy compared to our best estimate, which is a composite method akin to W4 theory. The error of CCSD(T) is thus much lower than for atomization energies. MP2 is surprisingly accurate for these systems with an RMS error of 1.3 kJ/mol. MP2.5 yields a clear improvement over MP2 (RMS of 0.5 kJ/mol) but still has an error about 3 times as large as CCSD(T) for the absolute RMS and almost 10 times as large for the relative RMS error. Neither SCS-MP2, SOS-MP2, nor DFT-SAPT yield lower errors than MP2. With a ΔCCSD(T) correction to MP2, the basis set limit is readily achieved when employing diffuse functions-without these, the convergence is rather slow.

The performance of a wide variety of DFT exchange-correlation functionals for a number of late-transition-metal reaction profiles has been considered. Benchmark ab-initio reference data for the prototype reactions Pd + H2, Pd + CH4, Pd + C2H6 (both C-C and C-H activation), and Pd + CH3Cl are presented, while ab-initio data of lesser quality were obtained for the catalytic hydrogenation of acetone and for the low-oxidation-state and high-oxidation-state mechanisms of the Heck reaction. "Kinetics" functionals such as mPW1K, PWB6K, BB1K, and BMK clearly perform more poorly for late-transition-metal reactions than for main-group reactions, as well as compared to general-purpose functionals. There is no single "best functional" for late-transition-metal reactions, but rather a cluster of several functionals (PBE0, B1B95, PW6B95, and TPSS25B95) that perform about equally well; if main-group thermochemical performance is additionally considered, then B1B95 and PW6B95 emerge as the best performers. TPSS25B95 and TPSS33B95 offer attractive performance compromises if weak interactions and main-group barrier heights, respectively, are also important. In the ab-initio calculations, basis set superposition errors (BSSE) can be greatly reduced by ensuring that the metal spd shell has sufficient radial flexibility in the high-exponent range. Optimal HF percentages in hybrid functionals depend on the class of systems considered, increasing from anions to neutrals to cations to main-group barrier heights; transition-metal barrier heights represent an intermediate situation. The use of meta-GGA correlation functionals appears to be quite beneficial.

In a previous contribution (Mol. Phys. {\bf 103}, xxxx, 2005), we established the suitability of density functional theory (DFT) for the calculation of molecular anharmonic force fields. In the present work, we have assessed a wide variety of basis sets and exchange-correlation functionals for harmonic and fundamental frequencies, equilibrium and ground-state rotational constants, and thermodynamic functions beyond the RRHO (rigid rotor-harmonic oscillator) approximation. The fairly good performance of double-zeta plus polarization basis sets for frequencies results from an error compensation between basis set incompleteness and the intrinsic error of exchange-correlation functionals. Triple-zeta plus polarization basis sets are recommended, with an additional high-exponent $d$ function on second-row atoms. All conventional hybrid GGA functionals perform about equally well: high-exchange hybrid GGA and meta-GGA functionals designed for kinetics yield poor results, with the exception of of the very recently developed BMK functional which takes a middle position along with the HCTH/407 (second generation GGA) and TPSS (meta-GGA) functionals. MP2 performs similarly to these functionals but is inferior to hybrid GGAs such as B3LYP and B97-1., Int. J. Quantum Chem., in press (special issue on vibrational spectroscopies)

Anharmonic force fields and vibrational spectra of the azabenzene series (pyridine, pyridazine, pyrimidine, pyrazine, s-triazine, 1,2,3-triazine, 1,2,4-triazine and s-tetrazine) and benzene are obtained using density functional theory (DFT) with the B97-1 exchange-correlation functional and a triple-zeta plus double polarization (TZ2P) basis set. Overall, the fundamental frequencies computed by second-order rovibrational perturbation theory are in excellent agreement with experiment. The resolution of the presently calculated anharmonic spectra is such that they represent an extremely useful tool for the assignment and interpretation of the experimental spectra, especially where resonances are involved., Comment: J. Phys. Chem. A, in press (jp0369589); supplementary material (quartic force fields in machine-readable format) available at http://theochem.weizmann.ac.il/web/papers/azabenzenes.html

New density functionals, using the kinetic-energy density Tau are reported. The newly introduced variable enhances the performance of previous functionals, leading to highly accurate functionals with and without the use of exact exchange. All these functionals are compared to commonly used functionals for a large test set, looking also at reactions and hydrogen bonded systems. Furthermore, their physical plausibility is discussed.

We consider tunneling transport between two parallel phase-coherent quantum wires with a magnetic field applied perpendicular to the plane of the wires. In the strong-tunneling regime, magnetic field can be used to tune coherent charge oscillations between the two wires. Magnetotunneling provides a momentum-resolved spectroscopic probe in the opposite limit of weak tunneling. In particular, it could be used to observe the dynamical separation of electronic charge and spin degrees of freedom that is predicted to occur in interacting one-dimensional systems.

Density functional theory (DFT) has become more successful at introducing dispersion interactions, and can be thus applied to a wide range of systems. Amongst these are systems that contain hydrogen bonds, which are extremely important for the biological regime. Here, the description of hydrogen-bonded interactions by DFT with and without dispersion corrections is investigated. For small complexes, for which electrostatics are the determining factor in the intermolecular interactions, the inclusion of dispersion with most functionals yields large errors. Only for larger systems, in which van der Waals interactions are more important, do dispersion corrections improve the performance of DFT for hydrogen-bonded systems. None of the studied functionals, including double hybrid functionals (with the exception of DSD-PBEP86 without dispersion corrections), are more accurate than MP2 for the investigated species.

Infrared photodissociation is used to record the vibrational spectrum of FeO2 (+)(He)2-4 which shows three bands at 1035, 980, and 506 cm(-1). Quantum chemical multi-reference configuration interaction calculations (MRCISD) of structures and harmonic frequencies show that these bands are due to two different isomers, an inserted dioxo complex with Fe in the +V oxidation state and a side-on superoxo complex with Fe in the +II oxidation state. These two are separated by a substantial barrier, 53 kJ/mol, whereas the third isomer, an end-on complex between Fe(+) and an O2 molecule, is easily converted into the side-on complex. For all three isomers, states of different spin multiplicity have been considered. Our best energies are computed at the MRCISD+Q level, including corrections for complete active space and basis set extension, core-valence correlation, relativistic effects, and zero-point vibrational energy. The average coupled pair functional (ACPF) yields very similar energies. Density functional theory (DFT) differs significantly from our best estimates for this system, with the TPSS functional yielding the best results. The other functionals tested are BP86, PBE, B3LYP, TPSSh, and B2PLYP. Complete active space second order perturbation theory (CASPT2) performs better than DFT, but less good than ACPF.

A new “HCTH” generalized gradient approximation (GGA) functional is presented. Its 15 parameters have been refined against data from a training set containing 407 atomic and molecular systems. We believe that the much enhanced training set means that the new functional HCTH/407 has a much greater universality than previous GGA functionals. Statistical data is presented for the 407 set for the new functional, as well as other functionals.

New generalized gradient approximation (GGA) functionals are reported, using the expansion form of A. D. Becke, J. Chem. Phys. 107, 8554 (1997), with 15 linear parameters. Our original such GGA functional, called HCTH, was determined through a least squares refinement to data of 93 systems. Here, the data are extended to 120 systems and 147 systems, introducing electron and proton affinities, and weakly bound dimers to give the new functionals HCTH/120 and HCTH/147. HCTH/120 has already been shown to give high quality predictions for weakly bound systems. The functionals are applied in a comparative study of the addition reaction of water to formaldehyde and sulfur trioxide, respectively. Furthermore, the performance of the HCTH/120 functional in Car–Parrinello molecular dynamics simulations of liquid water is encouraging.

We study electron transport through single and double quantumdots with large level spacing and charging energy. Motivatedby recent experiments we focus on linear and nonlinearresponse of two model systems: a single dot with two levelsand a capacitively coupled double dot. At low temperature andstrong coupling to the leads, quantum fluctuations and Kondo-like many-body effects become important and show up, e.g., asresonances in the current-voltage characteristics. Inparticular, we propose a way to observe the splitting of theKondo peak as a function of the applied bias voltage.

Comparisons with the results of coupled cluster calculations were made to assess the quality of density functionals in predicting the electronic binding energies of H-bonded complexes. A variety of different density functionals, namely B3LYP, B97-1, PBE0, HCTH, BLYP, PBE, LDA and a recently derived improvement of the HCTH functional (HCTH38), as well as the standard abinitio Hartree–Fock and second-order Moller–Plesset perturbation theory methods were applied using a triple-ζ plus double polarisation basis set. Equilibrium structures, counterpoise corrected binding energies and harmonic frequencies were calculated for the (HF)2, (HCl)2, (H2O)2, (CO)(HF), (OC)(HF), (FH)(NH3), (ClH)(NH3), (H2O)(NH3) and (H3O+)(H2O) complexes. Although the hybrid methods performed well in general, the new HCTH38 functional as a pure GGA predicted binding energies of better quality than the B3LYP functional. Bond length changes and frequency shifts were compared to MP2 results.

Following our earlier work on the subject, we have carried out density functional theory (DFT) and second-order Moller-Plesset perturbation theory (MP2) calculations of the dissociation energy of the reaction C60 yields C58 + C2 using polarized basis sets and geometries optimized with DFT methods. The present theoretical results support an electronic fragmentation energy D(sub e) around 10-11 eV in disagreement with most experimental results that place the dissociation energy D(sub o) (including zero point energy) around 7-8 eV. The plausible errors remaining in the theoretical calculations are unlikely to account for this big difference (2-4 eV).

Ethyl acetate (ethyl ethanoate) was crystallized in situ and the crystal structure was determined. In the solid, the molecule is flat with trans conformation. The geometric details of ethyl acetate as a solvate are analyzed statistically using the Cambridge Structural Database, uncovering a high degree of hidden disorder. Despite the disorder, they exhibit a preference of the trans over the gauche isomer, with a negligible contribution of the cis isomer. These results are compared to ab initio calculations on both solid-state and molecular level. For the molecular structures, the computed energy differences of the isomers match the statistics found as a solvent. Several DFT-D2 methods used to calculate the solid state yield results that differ significantly from the experiment.