The accuracy of ab initio molecular geometries for systems containing second-row atoms

The performance of the standard hierarchy of ab initio models--that is, Hartree-Fock theory, second-order Moller-Plesset theory, coupled-cluster singles-and-doubles theory, and coupled-cluster singles-doubles-approximate-triples theory--in combination with correlation-consistent basis sets is investigated for equilibrium geometries of molecules containing second-row elements. From an analysis on a collection of 31 molecules (yielding statistical samples of 41 bond distances and 13 bond angles), the statistical errors (mean deviation, mean absolute deviation, standard deviation, and maximum absolute deviation) are established at each level of theory. The importance of core correlation is examined by comparing calculations in the frozen-core approximation with calculations where all electrons are correlated.     

Scattering spherical voids in nanocrystalline TiO2- enhancement of efficiency in dye-sensitized solar cells

Spherical voids as light scattering centers in nanocrystalline TiO2 films were realized with polystyrene particles of diameter 400 nm, thus enhancing the photovoltaic performance by 25% on large areas, as well as providing an indication that these films can be used with electrolytes of higher viscosity.     

Semicanonical bases and preprojective algebras

We study the multiplicative properties of the dual of Lusztig's semicanonical basis. The elements of this basis are naturally indexed by the irreducible components of Lusztig's nilpotent varieties, which can be interpreted as varieties of modules over preprojective algebras. We prove that the product of two dual semicanonical basis vectors ρZ^′ and ρZ^″ is again a dual semicanonical basis vector provided the closure of the direct sum of the corresponding two irreducible components Z^′ and Z^″ is again an irreducible component. It follows that the semicanonical basis and the canonical basis coincide if and only if we are in Dynkin type An with n?4. Finally, we provide a detailed study of the varieties of modules over the preprojective algebra of type A₅. We show that in this case the multiplicative properties of the dual semicanonical basis are controlled by the Ringel form of a certain tubular algebra of type (6,3,2) and by the corresponding elliptic root system of type .     

Localized subharmonic waves in a circularly vibrated granular bed

Localized period-doubling waves arise in circularly shaken granular beds contained in an annular channel. These solitary wave packets are accompanied by a locally increased particle density. The width and velocity of the granular wave pulse are measured as a function of the bed height. A continuum model for the material distribution, based on the measured granular transport velocity as a function of the bed thickness, captures the essence of the experimental findings.     

Distributed memory parallel implementation of energies and gradients for second-order Møller-Plesset perturbation theory with the resolution-of-the-identity approximation

We present a parallel implementation of second-order M?ller-Plesset perturbation theory with the resolution-of-the-identity approximation (RI-MP2). The implementation is based on a recent improved sequential implementation of RI-MP2 within the Turbomole program package and employs the message passing interface (MPI) standard for communication between distributed memory nodes. The parallel implementation extends the applicability of canonical MP2 to considerably larger systems. Examples are presented for full geometry optimizations with up to 60 atoms and 3300 basis functions and MP2 energy calculations with more than 200 atoms and 7000 basis functions.     

Assignment and extraction of dynamics of a small molecule with a complex vibrational spectrum: thiophosgene

The dispersed fluorescence spectrum of the ground electronic state of thiophosgene, SCCl2, is analyzed in a very complex region of vibrational excitation, 7000-9000 cm(-1). The final result is that most of the inferred excited vibrational levels are assigned in terms of approximate constants of the motion. Furthermore, each level is associated with a rung on a ladder of quantum states on the basis of common reduced dimension fundamental motions. The resulting ladders cannot be identified by any experimental means, and it is the interspersing in energy of their rungs that makes the spectrum complex even after the process of level separation into polyads. Van Vleck perturbation theory is used to create polyad constants of the motion and a spectroscopic Hamiltonian from a potential fitted to experimental data. The eigen functions of this spectroscopic Hamiltonian are rewritten as semiclassical wave functions and transformed to a representation that allows us to analyze and assign the spectra with no other work other than to utilize concepts from nonlinear dynamics.     

Structural evolution of anionic silicon clusters SiN (20 <or= N <or= 45)

Results of a combined photoelectron spectroscopy and first-principles density-functional study of SiN- clusters in the size range 20 or= 20. For 28 相似文献