4,129 research outputs found
Potential surfaces for O atom-polymer reactions
Ab initio quantum chemistry methods are used to study the energetics of interactions of O atoms with organic compounds. Polyethylene (CH2)n has been chosen as the model system to study the interactions of O(3P) and O(1D) atoms with polymers. In particular, H abstraction is investigated and polyethylene is represented by a C3 (propane) oligomeric model. The gradient method, as implemented in the GRADSCF package of programs, is used to determine the geometries and energies of products and reactants. The saddle point, barrier geometry is determined by minimizing the squares of the gradients of the potential with respect to the internal coordinates. To correctly describe the change in bonding during the reaction at least a two configuration MCSCF (multiconfiguration self consistent field) or GVB (generalized valence bond) wave function has to be used. Basis sets include standard Pople and Dunning sets, however, increased with polarization functions and diffuse p functions on both the C and O atoms. The latter is important due to the O(-) character of the wave function at the saddle point and products. Normal modes and vibrational energy levels are given for the reactants, saddle points and products. Finally, quantitative energetics are obtained by implementing a small CAS (complete active space) approach followed by limited configuration interaction (CI) calculations. Comparisons are made with available experimental data
Statistical Geometry of Packing Defects of Lattice Chain Polymer from Enumeration and Sequential Monte Carlo Method
Voids exist in proteins as packing defects and are often associated with
protein functions. We study the statistical geometry of voids in
two-dimensional lattice chain polymers. We define voids as topological features
and develop a simple algorithm for their detection. For short chains, void
geometry is examined by enumerating all conformations. For long chains, the
space of void geometry is explored using sequential Monte Carlo importance
sampling and resampling techniques. We characterize the relationship of
geometric properties of voids with chain length, including probability of void
formation, expected number of voids, void size, and wall size of voids. We
formalize the concept of packing density for lattice polymers, and further
study the relationship between packing density and compactness, two parameters
frequently used to describe protein packing. We find that both fully extended
and maximally compact polymers have the highest packing density, but polymers
with intermediate compactness have low packing density. To study the
conformational entropic effects of void formation, we characterize the
conformation reduction factor of void formation and found that there are strong
end-effect. Voids are more likely to form at the chain end. The critical
exponent of end-effect is twice as large as that of self-contacting loop
formation when existence of voids is not required. We also briefly discuss the
sequential Monte Carlo sampling and resampling techniques used in this study.Comment: 29 pages, including 12 figure
A Two-Coordinate Nickel Imido Complex That Effects C−H Amination
An exceptionally low coordinate nickel imido complex, (IPr*)Ni═N(dmp) (2) (dmp = 2,6-dimesitylphenyl), has been prepared by the elimination of N_2 from a bulky aryl azide in its reaction with (IPr*)Ni(η^6-C_7H_8) (1). The solid-state structure of 2 features two-coordinate nickel with a linear C−Ni−N core and a short Ni−N distance, both indicative of multiple-bond character. Computational studies using density functional theory showed a Ni═N bond dominated by Ni(dπ)−N(pπ) interactions, resulting in two nearly degenerate singly occupied molecular orbitals (SOMOs) that are Ni−N π* in character. Reaction of 2 with CO resulted in nitrene-group transfer to form (dmp)NCO and (IPr*)Ni(CO)_3 (3). Net C−H insertion was observed in the reaction of 2 with ethene, forming the vinylamine (dmp)NH(CH═CH_2) (5) via an azanickelacyclobutane intermediate, (IPr*)Ni{N,C:κ^2-N(dmp)CH_2CH_2} (4)
NMR shieldings from density functional perturbation theory: GIPAW versus all-electron calculations
We present a benchmark of the density functional linear response calculation
of NMR shieldings within the Gauge-Including Projector-Augmented-Wave method
against all-electron Augmented-Plane-Wavelocal-orbital and uncontracted
Gaussian basis set results for NMR shieldings in molecular and solid state
systems. In general, excellent agreement between the aforementioned methods is
obtained. Scalar relativistic effects are shown to be quite large for nuclei in
molecules in the deshielded limit. The small component makes up a substantial
part of the relativistic corrections.Comment: 3 figures, supplementary material include
Magnetic groundstate and Fermi surface of bcc Eu
Using spin-spiral technique within the full potential linearized
augmented-plane-waves (LAPW) electronic structure method we investigate the
magnon spectrum and N\'eel temperature of bcc Eu. Ground state corresponding to
an incommensurate spin-spiral is obtained in agreement with experiment and
previous calculations. We demonstrate that the magnetic coupling is primarily
through the intra-atomic and exchange and
Ruderman-Kittel-Kasuya-Yosida mechanism. We show that the existence of this
spin-spiral is closely connected to a nesting feature of the Fermi surface
which was not noticed before.Comment: 6 pages 8 figure
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