Modeling the noble metal/TiO\u3csub\u3e2\u3c/sub\u3e (110) interface with hybrid DFT functionals: A periodic electrostatic embedded cluster model study

The interaction of Aun and Ptn (n=2,3) clusters with the stoichiometric and partially reduced rutile TiO2 (110) surfaces has been investigated using periodic slab and periodic electrostatic embedded cluster models. Compared to Au clusters, Pt clusters interact strongly with both stoichiometric and reduced TiO2 (110) surfaces and are able to enhance the reducibility of the TiO2 (110) surface, i.e., reduce the oxygen vacancy formation energy. The focus of this study is the effect of Hartree–Fock exchange on the description of the strength of chemical bonds at the interface of Au/Pt clusters and the TiO2 (110) surface. Hartree–Fock exchange helps describing the changes in the electronic structures due to metal cluster adsorption as well as their effect on the reducibility of the TiO2surface. Finally, the performance of periodic embedded cluster models has been assessed by calculating the Pt adsorption and oxygen vacancy formation energies. Cluster models, together with hybrid PBE0 functional, are able to efficiently compute reasonable electronic structures of the reduced TiO2surface and predict charge localization at surface oxygen vacancies, in agreement with the experimental data, that significantly affect computed adsorption and reaction energies

π-systems as lithium/hydrogen bond acceptors: Some theoretical observations

Ab initio calculations at the Hartree–Fock and correlated levels and density functional theory calculations have been performed with 6-31++G(d,p) and 6-311++G(d,p)basis sets on LiF and HF complexes of benzene, ethylene, and acetylene. Complex binding energies have been corrected for basis set superposition error, and zero point energy corrections have been done on Hartree–Fock binding energies. Computed results indicate that the complexes exist in different conformations and among them those with π-lithium and π-hydrogen bonds are the most stable. π-lithium bonds are stronger than π-hydrogen bonds. The computed binding energies and geometry of HF complexes correlate well with the available experimental results. LiF complexes with these π systems are found to be weaker than Li+ complexes but they are stronger than Li atom complexes. Natural bond orbital analysis traces the origin of the weak interactions that stabilize the complex. Li, as found in earlier cases, prefers the most symmetric site for interaction whereas proton prefers a nonsymmetric site in benzene complexes. Surprisingly, such a change of interaction geometry in LiF and HF complexes is found to change the donating π-orbitals in the benzene complexes

Nitroalkane Anomaly: Computational Study with Cluster and Continuum Modeling

The origin of anomalous relation between rates and equilibria for the proton-transfer reactions of nitroalkanes, known as nitroalkane anomaly, was investigated by theoretical calculations with a cluster model, in which three water molecules are explicitly considered in the system, as well as the PCM solvent continuum model. For the CH3NO2/CH3CH2NO2 system, B3LYP and MP2 computations reproduced the anomaly, and the imbalance in the charge distribution at the transition state (TS) was observed. In contrast, although the TS imbalance was detected for the substituted phenylnitromethane system, the Brønsted plots did not show any anomaly. The experimentally observed abnormally large Brønsted coefficient (a ~ 1.4) for this system does not arise from the charge imbalance at the saddle point structure, but is likely due to the effect of the reaction dynamics

\u3ci\u3eAb Initio\u3c/i\u3e and DFT Investigations of Lithium/Hydrogen Bonded Complexes of Trimethylamine, Dimethyl Ether and Dimethyl Sulfide

Ab initio and DFT computations have been carried out on LiF and HF complexes of a set of n-donors viz. trimethylamine, dimethyl ether and dimethyl sulfide with a 6-31++G(d,p) basis set. The effect of correlation has been included with MP2, MP4 and DFT calculations. NBO analyses of the wavefunctions have been performed to examine the intermolecular interaction at the orbital level. Calculations reveal that these donors form strong n→σ* complexes and computed binding energies of the (CH3)2O···HF complex agree very well with the experimental binding energies from IR spectroscopy. LiF forms stronger complexes than HF, and the effect of correlation on the hydrogen bond energy is considerable compared to the lithium bond energy. Though charge transfer interaction contributes to the stability of both LiF and HF complexes, it plays a less dominant role in lithium bonded complexes. While amine and ether donate their nσlone pair, sulfide donates an nπ lone pair and this results in perpendicular intermolecular bonds in sulfide complexes

Lithium bonding interaction in \u3ci\u3eH\u3csub\u3e2\u3c/sub\u3e\u3c/i\u3eCY⋯LiF \u3ci\u3e(Y\u3c/i\u3e=O,S\u3ci\u3e)\u3c/i\u3e complexes: A theoretical probe

Ab initio calculations at 6-31++G(d,p) level have been done on H2CY⋯LiF (Y=O,S) complexes choosing ten possible orientations in each complex. The effect of correlation on complex binding energies has been studied via single point MP2 (full) calculations done on 6-31++G(d,p) geometry. Binding energies have been corrected for basis set superposition error. Frequency calculations confirm that H2CO⋯LiF and H2CS⋯LiF complexes have three and two stable forms, respectively. The most stable form in each complex has been found to have a strong lithium bonding interaction and a secondary hydrogen bondinginteraction. NBO analysis has revealed that in this form oxygen donates nσ lone pair while sulfur donates its nπlone pair. In yet another stable form of these complexes, mixed donation of π and nσ electrons have been observed

Dynamic path bifurcation for the Beckmann reaction: observation and implication

The reaction of oximes to amides, known as the Beckmann rearrangement, may undergo fragmentation to form carbocations + nitriles instead of amides when the cations have reasonable stability. The reactions of oxime derivatives of 1-substituted-phenyl-2-propanones and 3-substituted-phenyl-2-butanones in aqueous solvents gave both rearrangement and fragmentation products, the ratio of which was dependent on substituents. Transition state (TS) optimizations and intrinsic reaction coordinate (IRC) calculations for the reaction of 1-phenyl-2-propanone oximes showed that there is a single TS for each substituted compound. The IRC path from the TS either led to a rearrangement product or a fragmentation product depending on the substituent; the IRC path changes from rearrangement to fragmentation when substituent X becomes more electron donating. Ab initio dynamics simulations were found to follow the IRC path for X = p-NH2 and p-MeO giving fragmentation products, and almost so for X = p-NO2 giving the rearrangement products. However, in a borderline case where X is less donating than p-MeO or less withdrawing than p-NO2, the trajectories did not follow the minimum energy path on the potential energy surface, but gave both rearrangement and fragmentation products directly from the single TS. This is a novel example of path bifurcation for a closed shell anionic reaction. It was concluded that a reactivity-selectivity argument based on the traditional TS theory may not always be applicable even to a well-known textbook organic reaction

\u3ci\u3eAb Initio\u3c/i\u3e Study of Formazan and 3-Nitroformazan

Formazan and 3-nitroformazan have been investigated at abinitio level (MP2/6-31G** and B3LYP/6-31G**) in all their possible conformations, for studying the various possibilities of intramolecular hydrogen bonding formation. The trans-syn-s-cis (TSSC), known also asyellowform, has been found to be the most stable conformer (at least in the gas phase) in both compounds. This particular structure is strongly stabilized by a N–H···N hydrogen bridge, which gives rise to a hexatomic chelate ring, with the possibility of a proton transfer process.This closely resembles that of malondialdehyde, previously studied, in the evolution of the potential energy shape but with a greater barrier height. Various approaches for obtaining a quantitative estimate of the energy of the hydrogen bridges are discussed. The electronic structures of the most favoured TSSC, TSST (trans-syn-s-trans) and TAST (trans-anti-s-trans) conformations of formazan have been compared with those of the corresponding forms of 1,5-diphenylformazan, in order to account for the UV spectra available in the literature and the different colours exhibited by the molecule on passing from one conformation to another

Integrated Computational Chemistry System for Catalysts Design

The understanding of valuable catalytic and adsorptive properties of heterogeneous catalysts at atomic and electronic levels is essential for the design of novel catalysts. Computer simulation studies can significantly contribute to provide a rational interpretation of the observed experimental results and suggest modification of new catalysts. Our recent work on the application of integrated computer simulation methods to investigate the structure and catalytic properties of solid surfaces including zeolites, transition metals and their oxides have been reviewed in this paper. We have emphasized the effectivity and applicability of integrated computer simulation system to solve the problems in a variety of targets of industrial and academic importance

Density functional theory study on the electronic structure of \u3ci\u3en\u3c/i\u3e- and \u3ci\u3ep\u3c/i\u3e-type doped SrTiO\u3csub\u3e3\u3c/sub\u3e at anodic solid oxide fuel cell conditions

The electronic conductivity and thermodynamic stability of mixed n-type and p-type doped SrTiO3 have been investigated at anodic solid oxide fuel cell (SOFC) conditions using density functional theory (DFT) calculations. In particular, constrained ab initio thermodynamic calculations have been performed to evaluate the phase stability and reducibility of various Nb- and Ga-doped SrTiO3 at synthesized and anodic SOFC conditions. The density of states (DOS) of these materials was analyzed to study the effects of n- and p-doping on the electronic conductivity. In agreement with experimental observations, we find that the transformation from 20% Nb-doped Sr-deficient SrTiO3 to a non-Sr-deficient phase occurs at high temperature and low oxygen partial pressure, which leads to a significant improvement in electronic conductivity. A mixed ionic/electronic conductor is obtained when doping 20% Nb-doped SrTiO3 with small amounts of Ga (10%) in a reducing environment and high temperature. Doping with higher concentrations of Ga, e.g., 20%, diminishes the electronic conductivity of the material. These findings suggest that independent of the specific dopant, mixed ionic/electronic conductivity can be obtained in perovskite oxides under reducing conditions and high temperatures by doping the B-site with small amounts of both n-type and p-type dopants