Even-tempered Slater-type orbitals revisited: from hydrogen to krypton

Even-tempered Slater-type orbital basis sets were developed in 1973, based on total atomic energy optimization. Here, we revisit ET STOs and propose new sets based on past experience and recent computational studies. From preliminary atomic and molecular tests, these sets are shown to be very well balanced and to perform, at lower cost, almost as well as a very large (close to complete) basis set.     

Optical properties of passivated silicon nanoclusters: the role of synthesis

The effect of preparation conditions on the structural and optical properties of silicon nanoparticles is investigated. Nanoscale reconstructions, unique to curved nanosurfaces, are presented for silicon nanocrystals and shown to have lower energy and larger optical gaps than bulk-derived structures. We find that high-temperature synthesis processes can produce metastable noncrystalline nanostructures with different core structures than bulk-derived crystalline clusters. The type of core structure that forms from a given synthesis process may depend on the passivation mechanism and time scale. The effect of oxygen on the optical of different types of silicon structures is calculated. In contrast to the behavior of bulklike nanostructures, for noncrystalline and reconstructed crystalline structures surface oxygen atoms do not decrease the gap. In some cases, the presence of oxygen atoms at the nanocluster surface can significantly increase the optical absorption gap, due to decreased angular distortion of the silicon bonds. The relationship between strain and the optical gap in silicon nanoclusters is discussed.     

4-metalated condensed pyrimidines: their preparation and reaction with aldehydes under Barbier-type conditions

[reaction: see text] The organometallic intermediate obtained from halogen-metal exchanges of 4-iodo-6-phenylthieno[2,3-d]pyrimidine under Barbier-type conditions was reacted with aldehydes to form the corresponding alcohols in moderate yields. The reaction involving an organolithium intermediate proceeded only at low temperature, whereas the reaction involving a magnesium ate intermediate also proceeded at room temperature. A crystal structure confirms that the expected constitutional alcohol isomer is formed, where no migration has taken place. The conditions were also suitable for 9-benzyl-6-iodopurine.     

Ultrafast molecular dissociation of water in ice

Using x-ray emission and photoemission spectroscopies to measure the occupied valence levels in a thin crystalline ice film, we resolve the ionization-induced dissociation of water in ice on a femtosecond time scale. Isotope substitution confirms proton transfer during the core-hole lifetime in spite of the nonresonant excitation. Through ab initio molecular dynamics on the core-ionized state, the dissociation and spectrum evolution are followed at femtosecond intervals. The theoretical simulations confirm the experimental analysis and allow for a detailed study of the dissociative reaction path.     

Rejection-free geometric cluster algorithm for complex fluids

We present a novel, generally applicable Monte Carlo algorithm for the simulation of fluid systems. Geometric transformations are used to identify clusters of particles in such a manner that every cluster move is accepted, irrespective of the nature of the pair interactions. The rejection-free and nonlocal nature of the algorithm make it particularly suitable for the efficient simulation of complex fluids with components of widely varying size, such as colloidal mixtures. Compared to conventional simulation algorithms, typical efficiency improvements amount to several orders of magnitude.     

Optimal topological test for degeneracies of real Hamiltonians

We consider adiabatic transport of eigenstates of real Hamiltonians around loops in parameter space. It is demonstrated that loops that map to nontrivial loops in the space of eigenbases must encircle degeneracies. Examples from Jahn-Teller theory are presented to illustrate the test. We show furthermore that the proposed test is optimal.     

Vibrational multilevel quantum coherence due to anharmonic couplings in intermolecular hydrogen bonds

Femtosecond three-pulse photon-echo studies of acetic acid dimers in solution reveal multilevel coherence of O-H stretching excitations caused by the anharmonic coupling between the high-frequency stretching and low-frequency hydrogen-bond motions. We demonstrate for the first time that such multilevel coherence determines the nonexponential decay of the macroscopic O-H stretching polarization, whereas spectral diffusion processes play a minor role. The dephasing time of individual vibrational transitions contributing to the overall polarization is approximately 200 fs.     

Effects of subfemtosecond quantum correlations in neutron scattering on water

Several recent experiments have shown that protons, and to some extent also deuterons, show anomalous cross sections when the neutrons have energies in the range 10-100 eV (this results in a Compton scattering process where an essential part of the energy is transferred to one of the scattering particles). Here, an experiment on partially deuterated water, carried out by Chatzidimitriou-Dreismann et al., is analyzed in terms of a theory, which assumes that during the short duration (<10(-15) s) of this scattering process, protons are exchange correlated and cannot be considered as independent scattering objects. The quantum decoherence time for protons in liquid water is estimated from a simple model for the interaction of the water protons with hydrogen bonds.