Assessment of density functional approximations for N and CO physisorption on benzene and graphene.

Experimental isotherms of N and CO on carbon-based porous materials and models of the physisorption of gases on surfaces are used to obtain the pore size distribution (PSD). An accurate modelization of the physisorption of N and CO on the surface of carbon-based porous materials is important to obtain accurate N and CO storage capacities and reliable PSDs. Physisorption depends on the dispersion interactions.

Structural Trends in Monoboronyl Compounds: Analysis of the Interaction of Second-Row Elements with BO.

A theoretical study of the monoboronyl compounds of second-row elements, [XBO] (X = Na, Si, P, S, Cl), has been carried out. It is observed that the preference for the XBO arrangement is higher when moving to the right of the period. In the case of sodium monoboronyl three minima were characterized, all lying rather close in energy: linear NaBO, linear NaOB, and an L-shaped structure.

Molecular Structure and Bonding in Plutonium Carbides: A Theoretical Study of PuC3.

The most relevant species of plutonium tricarbide were characterized using theoretical methods. The global minimum is predicted to be a fan structure where the plutonium atom is bonded to a quasi-linear C3 unit. A rhombic isomer, shown to be a bicyclic species with transannular C-C bonding, lies about 39 kJ/mol above the fan isomer.

Enhanced association for C70 over C60 with a metal complex with corannulene derivate ligands.

The geometry imposed by the coordination sphere around the metal, together with the choice of the "arms" can be advantageously used to build corannulene-based molecular tweezers, which show great affinities for C60 and C70, as revealed by NMR titration experiments, mass spectroscopy, DFT calculations and the single crystal X-ray structural analysis of the compound C60 ⊂1.

Halogen-abstraction reactions from chloromethane and bromomethane molecules by alkaline-earth monocations.

The reactions, in the gas phase, between alkali-earth monocations (Mg(+), Ca(+), Sr(+), Ba(+)) and CH3X (X = Cl, Br) have been theoretically studied. The stationary points on the potential energy surfaces were characterized at the Density Functional Theory level on the framework of the mPW1K functional with the QZVPP Ahlrichs's basis sets. A complementary kinetics study has also been performed using conventional/variational microcanonical transition state theory.

Kinetics studies of the reactions of main fourth-period monocations (Ga+, Ge+, As+, and Se+) with methyl fluoride.

Thermodynamics and kinetics theoretical studies on the gas-phase reactions of fluoromethane with main fourth-period monocations (Ga(+), Ge(+), As(+), and Se(+)) have been carried out. Density functional theory (in particular mPW1K functional) was employed in the description of the potential energy surfaces, and refinement of the energies were done at the CCSD(T) level. The reaction rate constants were estimated using variational/conventional microcanonical transition state theory.

Molecular structure of uranium carbides: isomers of UC3.

In this article, the most relevant isomers of uranium tricarbide are studied through quantum chemical methods. It is found that the most stable isomer has a fan geometry in which the uranium atom is bonded to a quasilinear C3 unit. Both, a rhombic and a ring CU(C2) structures are found about 104-125 kJ/mol higher in energy.

Reactivity of first-row transition metal monocations (Sc+, Ti+, V+, Zn+) with methyl fluoride: a computational study.

The gas-phase reactivity of methyl fluoride with selected first-row transition metal monocations (Sc(+), Ti(+), V(+), and Zn(+)) has been theoretically investigated. Our thermochemical and kinetics study shows that early transition-metal cations exhibit a much more active chemistry than the latest transition metal monocation Zn(+). The strong C-F bond in methyl fluorine can be activated by scandium, titanium, and vanadium monocations yielding the metal fluorine cation, MF(+).

Small carbides of third-row main group elements: structure and bonding in C3X compounds (X = K-Br).

The molecular structures of third-row main group tricarbides C(3)X (X = K-Br) have been studied by quantum chemical methods. It is found that less electronegative elements (K, Ca, Ga, Ge) favor either fan or rhombic structures (resulting from side interactions with either linear or triangular C(3) units), whereas the more electronegative elements (As, Se, Br) favor linear or three-membered ring structures (resulting from σ-type interactions with either linear or triangular C(3) units). The predicted global minima are of fan type for C(3)K, rhombic for C(3)Ca, C(3)Ga, and C(3)Ge, linear for C(3)As and C(3)Se, and a three-membered ring for C(3)Br.

On the molecular structure of uranium dicarbide: T-shape versus linear isomers.

A theoretical study of the molecular structure of uranium dicarbide has been carried out employing DFT, coupled cluster, and multiconfigurational methods. A triangular species, corresponding to a (5)A(2) electronic state, has been found to be the most stable UC(2) species. A triplet linear CUC species, which has been observed in recent infrared spectroscopy experiments, lies much higher in energy.

Computational study of the reaction of P+ with acetylene: does spin-crossing play a significant role?

A computational study of the reaction of P(+)((3)P) with acetylene has been carried out. The only exothermic products correlating with the reactants are PCCH(+)((2)Π) + H((2)S). Two different pathways leading to these products that are apparently barrier-free have been found.

Ab initio benchmark calculations on Ca(II) complexes and assessment of density functional theory methodologies.

A set of benchmark results for the geometries, binding energies, and protonation affinities of 24 complexes of small organic ligands with Ca(II) is provided. The chosen level of theory is CCSD(T)/CBS obtained by means of a composite procedure. The performance of four density functionals, namely, PW91, PBE, B3LYP, and TPSS and several Pople-type basis sets, namely, 6-31G(d), 6-31+G(d), 6-31+G(2d,p) and 6-311+G(d) have been assessed.

Structure and bonding in third-row main group dicarbides C2X (X=K-Br).

The molecular structures of third-row main group dicarbides C(2)X (X=K-Br) have been studied by theoretical methods. It is found that K, Ca, and Ga favor C(2v)-symmetric (T-shape) ground states, whereas As, Se, and Br have linear or quasilinear ground states. In the case of germanium.

Cyanide complexes of Ti(IV): a computational study.

Density functional theory (B3LYP) and coupled-cluster techniques [CCSD(T)] including solvent effects have been used to study the homoleptic and mixed cyanide/isocyanide complexes of Ti(IV), [Ti(CN)(n)](4-n) (n=1-6). The most stable isomer is found to be the isocyanide form except for n=6 where the cyanide isomer is preferred. Calculations accounting for solvent effects show that, irrespective of the solvent employed, the hexacyanocomplex should be formed.

Polyisocyanides of titanium.

Neutral Ti[CN](n) complexes have been investigated with quantum chemistry techniques. According to our theoretical predictions, these complexes are shown to prefer isocyanide arrangements. Therefore, these compounds are good candidates to be the first polyisocyanides to be characterized.

Gas-Phase Reaction of NH2(+) with Acetic Acid: Implications in Astrochemistry.

A theoretical study of the ion-molecule reaction, NH2(+) with acetic acid that could lead to precursors of glycine in the interstellar medium, has been carried out on the triplet and singlet potential energy surfaces. All stationary points and transition states on the (NO2C2H6)(+) triplet and singlet surfaces have been determined at the MP2(full) level with the cc-pVTZ basis set. Energetic data have been obtained at the CCSD(T) level employing the aug-cc-pVTZ basis set.

Monoligand Zn(II) Complexes: Ab Initio Benchmark Calculations and Comparison with Density Functional Theory Methodologies.

A systematic theoretical study on several models of Zn(II) complexes has been carried out employing both ab initio correlated wave function and density functional methods. The performance of five different functionals namely PW91, PBE, B3LYP, MPWLYP1M, and TPSS in the prediction of metal-ligand bond distances, binding energies, and proton affinities has been assessed comparing the results to those obtained with the MP2 and CCSD(T) wave function methodologies. Several basis sets ranging from double-ζ up to quintuple-ζ quality have been used, including the recently developed all-electron correlation consistent basis sets for zinc.

Cyanides and isocyanides of first-row transition metals: molecular structure, bonding, and isomerization barriers.

Cyanides and isocyanides of first-row transition metal M(CN) (M=Sc-Zn) are investigated with quantum chemistry techniques, providing predictions for their molecular properties. A careful analysis of the competition between cyanide and isocyanide isomers along the transition series has been carried out. In agreement with the experimental observations, late transition metals (Co-Zn) clearly prefer a cyanide arrangement.

Structure and bonding in first-row transition metal dicarbide cations MC2+.

A theoretical study of the first-row transition metal dicarbide cations MC2+ (M=Sc-Zn) has been carried out. Predictions for different molecular properties that could help in their eventual experimental detection have been made. Most MC2+ compounds prefer a C2v symmetric arrangement over the linear geometry.

A computational study of the reaction of ground-state nitrogen atoms with chloromethyl radicals.

A computational study of the N(4S) + CH2Cl reaction has been carried out. The first step of the reaction is the formation of an initial intermediate (NCH2Cl), which is relatively stable and does not involve any energy barrier. The two most exothermic products are those resulting from the release of a chlorine atom, H2C=N + Cl and trans-HC=NH + Cl.

Structure and bonding in first-row transition-metal dicarbides: are they related to the stability of met-cars?

First-row transition-metal dicarbides MC(2) (M=Sc-Zn) have been investigated by using quantum-mechanical techniques. The competition between cyclic and linear isomers in these systems has been studied and the bonding scheme for these compounds is discussed through topological analysis of electron density. All of the systems have been found to prefer a C(2v)-symmetric arrangement, although for ZnC(2) the energy difference between this and the linear isomer is rather small.

Computational study of the reaction of N(2D) atoms with CH2F radicals: an example of a barrier-free reaction involving very high internal energies.

The singlet potential-energy surface for the N(2D)+CH2F(2A') reaction has been studied employing both second-order Møller-Plesset and density-functional theories. The energies of the involved species have been refined using the Gaussian-2, complete basis set, and coupled-cluster singles and doubles (triples) methods. The reaction proceeds through the formation of an initial intermediate, which does not involve any activation barrier.

Pseudorotation motion in tetrahydrofuran: an ab initio study.

The use of different models based on experimental information about the observed level splitings, rotational constants, and far-infrared transition frequencies leads to different predictions on the equilibrium geometry for tetrahydrofuran. High-level ab initio calculations [coupled cluster singles, doubles (triples)/complete basis set (second order Moller-Plesset triple, quadrupole, quintuple)+zero-point energy(anharmonic)] suggest that the equilibrium conformation of tetrahydrofuran is an envelope C(s) structure. The theoretical geometrical parameters might be helpful to plan further microwave spectroscopic studies in order to get a physical interpretation of the measurements.

Molecular structures, bond energies, and bonding analysis of group 11 cyanides TM(CN) and isocyanides TM(NC) (TM = Cu, Ag, Au).

We report on quantum chemical calculations at the DFT (BP86/TZP) and ab initio (CCSD(T)/III+) levels of the title compounds. The geometries, vibrational spectra, heats of formation, and homolytic and heterolytic bond dissociation energies are given. The calculated bond length of Cu-CN is in reasonable agreement with experiment.

Structures, bond energies, heats of formation, and quantitative bonding analysis of main-group metallocenes [E(Cp)2] (E = Be-Ba, Zn, Si-Pb) and [E(Cp)] (E = Li-Cs, B-Tl).

The geometries, metal-ligand bond dissociation energies, and heats of formation of twenty sandwich and half-sandwich complexes of the main-group elements of Groups 1, 2, 13, and 14, and Zn have been calculated with quantum chemical methods. The geometries of the [E(Cp)] and [E(Cp)2] complexes were optimized using density functional theory at the BP86 level with valence basis sets, which have DZP and TZP quality. Improved energy values have been obtained by using coupled-cluster theory at the CCSD(T) level.