The correlation-consistent composite approach ͑ccCA͒, an ab initio composite technique for computing atomic and molecular energies, recently has been shown to successfully reproduce experimental data for a number of systems. The ccCA is applied to the G3/99 test set, which includes 223 enthalpies of formation, 88 adiabatic ionization potentials, 58 adiabatic electron affinities, and 8 adiabatic proton affinities. Improvements on the original ccCA formalism include replacing the small basis set quadratic configuration interaction computation with a coupled cluster computation, employing a correction for scalar relativistic effects, utilizing the tight-d forms of the second-row correlation-consistent basis sets, and revisiting the basis set chosen for geometry optimization. With two types of complete basis set extrapolation of MP2 energies, ccCA results in an almost zero mean deviation for the G3/99 set ͑with a best value of −0.10 kcal mol −1 ͒, and a 0.96 kcal mol −1 mean absolute deviation, which is equivalent to the accuracy of the G3X model chemistry. There are no optimized or empirical parameters included in the computation of ccCA energies. Except for a few systems to be discussed, ccCA performs as well as or better than Gn methods for most systems containing first-row atoms, while for systems containing second-row atoms, ccCA is an improvement over Gn model chemistries.

Collisions of hyperthermal oxygen atoms, with an average laboratory-frame translational energy of 520 kJ mol−1, on continuously refreshed ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([emim][NTf2]) and 1-dodecyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([C12mim][NTf2]), were studied with the use of a beam-surface scattering technique. Time-of-flight and angular distributions of inelastically scattered O and reactively scattered OH and H2O were collected for various angles of incidence with the use of a rotatable mass spectrometer detector. For both O and OH, two distinct scattering processes were identified, which can be empirically categorized as thermal and nonthermal. Nonthermal scattering is more probable for both O and OH products. The observation of OH confirms that at least some reactive sites, presumably alkyl groups, must be exposed at the surface. The ionic liquid with the longer alkyl chain, [C12mim][NTf2], is substantially more reactive than the liquid with the shorter alkyl chain, [emim][NTf2], and proportionately much more so than would be predicted simply from stoichiometry based on the number of abstractable hydrogen atoms. Molecular dynamics models of these surfaces shed light on this change in reactivity. The scattering behavior of O is distinctly different from that of OH. However, no such differences between inelastic and reactive scattering dynamics have been seen in previous work on pure hydrocarbon liquids, in particular, the benchmark, partially branched hydrocarbon, squalane (C30H62). The comparison between inelastic and reactive scattering dynamics indicates that inelastic scattering from the ionic liquid surfaces takes place predominantly at nonreactive sites that are effectively stiffer than the reactive alkyl chains, with a higher proportion of collisions sampling such sites for [emim][NTf2] than for [C12mim][NTf2].

The mechanical behavior of carbon nanotube (CNT)-based fibers and nanocomposites depends intimately on the shear interactions between adjacent tubes. We have applied an experimental-computational approach to investigate the shear interactions between adjacent CNTs within individual double-walled nanotube (DWNT) bundles. The force required to pull out an inner bundle of DWNTs from an outer shell of DWNTs was measured using in situ scanning electron microscopy methods. The normalized force per CNT-CNT interaction (1.7 ± 1.0 nN) was found to be considerably higher than molecular mechanics (MM)-based predictions for bare CNTs (0.3 nN). This MM result is similar to the force that results from exposure of newly formed CNT surfaces, indicating that the observed pullout force arises from factors beyond what arise from potential energy effects associated with bare CNTs. Through further theoretical considerations we show that the experimentally measured pullout force may include small contributions from carbonyl functional groups terminating the free ends of the CNTs, corrugation of the CNT-CNT interactions, and polygonization of the nanotubes due to their mutual interactions. In addition, surface functional groups, such as hydroxyl groups, that may exist between the nanotubes are found to play an unimportant role. All of these potential energy effects account for less than half of the ~1.7 nN force. However, partially pulled-out inner bundles are found not to pull back into the outer shell after the outer shell is broken, suggesting that dissipation is responsible for more than half of the pullout force. The sum of force contributions from potential energy and dissipation effects are found to agree with the experimental pullout force within the experimental error.

This work represents a synergistic experimental/computational study of the molecular spectroscopy and bonding in Au(CO)Cl in solution and the solid state. The luminescence behavior for crystalline solids is similar for Au(CO)Cl and related (RNC)AuCl complexes that likewise stack in infinite chains, and both exhibit orange-red unstructured phosphorescence bands with extremely large Stokes shifts ((15−20) × 103 cm-1). The long aurophilic distances computed for the ground state (∼3.2 Å) are contracted in the phosphorescent excited state (∼2.6 Å), demonstrating excimeric Au−Au covalent bonds. The spectral data suggest phosphorescent species in which the excimeric Au−Au bonding is extended beyond two adjacent molecules in the solid state. Controlling the concentration in frozen solutions attains phosphorescent bands due to dimeric species for which the emission energies are higher (in the blue region) than those for crystalline solids and are reproduced by ab initio calculations. The spectral findings herein suggest that predictive information about the supramolecular structure may be obtained by the luminescnce behavior. This is exemplified by crystals of (1,1,3,3-Me4BuNC)AuCl, whose red-orange luminsecence anticipated an extended-chain supramolecular structure, which was later verified crystallographically, as the molecules were found to pack in zigzag chains with alternating short (3.418 Å) and long (4.433 Å) aurophilic distances. Solutions of Au(CO)Cl exhibit negative deviation from Beer's law for, higher-energy monomer bands with the appearance of lower-energy bands at high concentrations due to the dimerization of molecules. Time-dependent density-functional theory (TD-DFT) calculations for monomer and dimer models show good agreement with the experimental spectra and account for the major absorption bands. Ab initio calculations (CCSD(T)/cc-pVTZ) show a blue shift of ∼23 cm-1 in the νC ⋮ O frequency upon complexation, thus providing the first computational evidence of this anomalous blue shift known experimentally for Au(CO)Cl.

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Advanced ab initio [coupled cluster theory through quasiperturbative triple excitations (CCSD(T))] and density functional (B3LYP) computational chemistry approaches were used in combination with the standard and augmented correlation consistent polarized valence basis sets [cc-pVnZ and aug-cc-pVnZ, where n=D(2), T(3), Q(4), and 5] to investigate the energetic and structural properties of small molecules containing third-row (Ga-Kr) atoms. These molecules were taken from the Gaussian-2 (G2) extended test set for third-row atoms. Several different schemes were used to extrapolate the calculated energies to the complete basis set (CBS) limit for CCSD(T) and the Kohn-Sham (KS) limit for B3LYP. Zero point energy and spin orbital corrections were included in the results. Overall, CCSD(T) atomization energies, ionization energies, proton affinities, and electron affinities are in good agreement with experiment, within 1.1 kcal/mol when the CBS limit has been determined using a series of two basis sets of at least triple zeta quality. For B3LYP, the overall mean absolute deviation from experiment for the three properties and the series of molecules is more significant at the KS limit, within 2.3 and 2.6 kcal/mol for the cc-pVnZ and aug-cc-pVnZ basis set series, respectively.

To better understand the reactivity of gases with liquid surfaces, experimentalists have recently probed the reactive scattering of atomic fluorine at the surface of liquid squalane (C(30)H(62)). In this paper we further this research by simulating this scattering process at collision energies of 0.5 and 1.0 eV using a hybrid QM/MM molecular dynamics scheme. To model the structure of the liquid surface, classical molecular dynamics calculations were performed utilizing the OPLS-AA force field. During the F + squalane molecular dynamics simulation, QM/MM calculations are performed at every trajectory step by combining the MSINDO semiempirical Hamiltonian with OPLS-AA and using a dynamic partitioning of the atoms in the QM or MM regions via a "seed atom" method. This computational model provides a type of "on-the-fly" direct dynamics applicable to larger scale chemical processes that include the making/breaking of chemical bonds not available in standard force field models. Our results show that H abstraction is the only reactive scattering pathway and that most trajectories result in reactive scattering. Reaction statistics at the squalane surface are discussed, including variation of the results with incident angle and collision energy, and the probability of reaction as a function of carbon atom type, collision depth, and residence time. Product states, including angular distributions and final translational and rovibrational energies, are also considered and found to be significantly affected by the exothermic reaction energy for H abstraction. The vibrational distributions are in good agreement with recent experiments, but the rotational distributions are dominated by a nonthermal component while the experiments, which involve thermal incident energies, show comparable thermal and nonthermal contributions. Results for O + squalane at 1.0 eV, which we also present, show analogous comparisons with experiment, with OH vibrational distributions which are cold and match experiment, while the calculated rotational distributions are dominated by nonthermal behavior.