Ab initio study of the (2 × 2) phase of barium on graphene

We present a first-principles density functional theory study on the structural, electronic and dynamical properties of a novel barium doped graphene phase. Low energy electron diffraction of barium doped graphene presents clear evidence of (2 × 2) spots induced by barium adatoms with BaC₈ stoichiometry. First principles calculations reveals that the phase is thermodynamically stable but unstable to segregation towards the competitive BaC₆ monolayer phase. The calculation of phonon spectrum confirms the dynamical stability of the BaC₈ phase indicating its metastability, probably stabilized by doping and strain conditions due to the substrate. Barium induces a relevant doping of the graphene π states and new barium-derived hole Fermi surface at the M-point of the (2 × 2) Brillouin zone. In view of possible superconducting phase induced by foreign dopants in graphene, we studied the electron–phonon coupling of this novel (2 × 2) obtaining λ = 0.26, which excludes the stabilization of a superconducting phase.     

BOLD signal sign and transient vessels volume variation

The purpose of this work was to investigate the relation between BOLD signal sign and transient vessels volume variation induced by apnea. This stimulus consisting of breath holding after inspiration is able to induce a light slowing down in venous blood flow like in a sort of Valsalva maneuver. We observed diffuse negative BOLD responding areas at cortical level and a stronger negative response in correspondence of the main sinuses. These phenomena seem to be unrelated to a specific neural activity, appearing to be expressions of a mechanical variation in the hemodynamics. Our study suggests that particular care must be considered in the interpretation of fMRI findings, especially when patients with vascular-related cerebral diseases are involved.     

Bone tissue and porous media: common features and differences studied by NMR relaxation

Despite significant differences between bone tissues and other porous media such as oilfield rocks, there are common features as well as differences in the response of NMR relaxation measurements to the internal structures of the materials. Internal surfaces contribute to both transverse (T2) and longitudinal (T1) relaxation of pore fluids, and in both cases the effects depend on, among other things, local surface-to-volume ratio (S/V). In both cases variations in local S/V can lead to distributions of relaxation times, sometimes over decades. As in rocks, it is useful to take bone data under different conditions of cleaning, saturation, and desaturation. T1 and T2 distributions are computed using UPEN. In trabecular bone it is easy to see differences in dimensions of intertrabecular spaces in samples that have been de-fatted and saturated with water, with longer T1 and T2 for larger pores. Both T1 and T2 distributions for these water-saturated samples are bimodal, separating or partly separating inter- and intratrabecular water. The T1 peak times have a ratio of from 10 to 30, depending on pore size, but for the smaller separations the distributions may not have deep minima. The T2 peak times have ratios of over 1000, with intratrabecular water represented by large peaks at a fraction of a ms, which we can observe only by single spin echoes. CPMG data show peaks at about a second, tapering down to small amplitudes by a ms. In all samples the free induction decay (FID) from an inversion-recovery (IR) T1 measurement shows an approximately Gaussian (solid-like) component, exp[-1/2 (T/TGC), with TGC approximately 11.7+/-0.7 micros (GC for "Gaussian Component"), and a liquid-like component (LLC) with initially simple-exponential decay at the rate-average time T(2-FID) for the first 100 micros. Averaging and smoothing procedures are adopted to derive T(2-FID) as a function of IR time and to get T1 distributions for both the GC and the LLC. It appears that contact with the GC, which is presumed to be 1H on collagen, leads to the T2 reduction of at least part of the LLC, which is presumed to be water. Progressive drying of the cleaned and water-saturated samples confirms that the long T1 and T2 components were in the large intertrabecular spaces, since the corresponding peaks are lost. Further drying leads to further shortening of T2 for the remaining water but eventually leads to lengthening of T1 for both the collagen and the water. After the intertrabecular water is lost by drying, T1 is the same for GC and LLC. T(2-FID) is found to be roughly 320/alpha micros, where alpha is the ratio of the extrapolated GC to LLC, appearing to indicate a time tau of about 320 micros for 1H transverse magnetization in GC to exchange with that of LLC. This holds for all samples and under all conditions investigated. The role of the collagen in relaxation is confirmed by treatment to remove the mineral component, observing that the GC remains and has the same TGC and has the same effect on the relaxation times of the associated water. Measurements on cortical bone show the same collagen-related effects but do not have the long T1 and T2 components.     

Homogenization of a graphene sheet

A continuum model for a graphene sheet undergoing infinitesimal in-plane deformations is derived by applying the arguments of homogenization theory. The model turns out to coincide with that found by various authors with different methods, but it avoids anticipations on the validity of any properly adjusted or generalized Cauchy–Born rule. The constitutive equation for stress and the effective Young’s modulus and Poisson ratio are explicitly given in terms of the bond constants.     

CRYSCOR: a program for the post-Hartree-Fock treatment of periodic systems

Cryscor is a periodic post-Hartree-Fock program based on local functions in direct space, i.e., Wannier functions and projected atomic orbitals. It uses atom centered Gaussians as basis functions. The Hartree-Fock reference, as well as symmetry information, is provided by the Crystal program. Cryscor presently features an efficient and parallel implementation of periodic local second order M?ller-Plesset perturbation theory (MP2), which allows us to study 1D-, 2D- and 3D-periodic systems beyond 1000 basis functions per unit cell. Apart from the correlation energy also the MP2 density matrix, and from that the Compton profile, are available. Very recently, a new module for calculating excitonic band gaps at the uncorrelated Configuration-Interaction-Singles (CIS) level has been added. Other advancements include new extrapolation techniques for calculating surface adsorption on semi-infinite solids. In this paper the diverse features and recent advances of the present Cryscor version are illustrated by exemplary applications to various systems: the adsorption of an argon monolayer on the MgO (100) surface, the rolling energy of a boron nitride nanoscroll, the relative stability of different aluminosilicates, the inclusion energy of methane in methane-ice-clathrates, and the effect of electron correlation on charge and momentum density of α-quartz. Furthermore, we present some first tentative CIS results for excitonic band gaps of simple 3D-crystals, and their dependence on the diffuseness of the basis set.     

Fiscal policy lags and income adjustment processes

The interest in the impact of fiscal policy lags on economic stability increased in the last decade. Several studies have been made on delays either in the government expenditure or in the tax system, where lags exist between the accrual and the payment of taxes. Nevertheless there is in the literature no model where time delays in government expenditures and in tax revenues are considered together as it happens in the real world. In this paper we remedied this defect and proposed a macro-dynamic model where two delays appear: the first pertains to the public expenditure, the second, to the tax revenue. The resulting system of delayed differential equations is studied qualitatively and numerically. The analysis suggests that only particular combinations of the two delays make the system stable. Prevalently the system is unstable and chaotic motions may arise. This implies that the economy may need appropriate structural changes in the public sector to improve fiscal policy outcomes in such a way they may really be consistent with their stabilization purposes.     

Mathematical Tool from Corn Stover TGA to Determine Its Composition

Corn stover was treated by steam explosion process at four different temperatures. A fraction of the four exploded matters was extracted by water. The eight samples (four from steam explosion and four from water extraction of exploded matters) were analysed by wet chemical way to quantify the amount of cellulose, hemicellulose and lignin. Thermogravimetric analysis in air atmosphere was executed on the eight samples. A mathematical tool was developed, using TGA data, to determine the composition of corn stover in terms of cellulose, hemicellulose and lignin. It uses the biomass degradation temperature as multiple linear function of the cellulose, hemicellulose and lignin content of the biomass with interactive terms. The mathematical tool predicted cellulose, hemicellulose and lignin contents with average absolute errors of 1.69, 5.59 and 0.74?%, respectively, compared to the wet chemical method.     

Rhodium-catalyzed asymmetric hydrogenation of olefins with PhthalaPhos, a new class of chiral supramolecular ligands

A library of 19 binol-derived chiral monophosphites that contain a phthalic acid diamide group (PhthalaPhos) has been designed and synthesized in four steps. These new ligands were screened in the rhodium-catalyzed enantioselective hydrogenation of prochiral dehydroamino esters and enamides. Several members of the library showed excellent enantioselectivity with methyl 2-acetamido acrylate (6 ligands gave >97% ee), methyl (Z)-2-acetamido cinnamate (6 ligands gave >94% ee), and N-(1-phenylvinyl)acetamide (9 ligands gave >95% ee), whilst only a few representatives afforded high enantioselectivities for challenging and industrially relevant substrates N-(3,4-dihydronaphthalen-1-yl)-acetamide (96% ee in one case) and methyl (E)-2-(acetamidomethyl)-3-phenylacrylate (99% ee in one case). In most cases, the new ligands were more active and more stereoselective than their structurally related monodentate phosphites (which are devoid of functional groups that are capable of hydrogen-bonding interactions). Control experiments and kinetic studies were carried out that allowed us to demonstrate that hydrogen-bonding interactions involving the diamide group of the PhthalaPhos ligands strongly contribute to their outstanding catalytic properties. Computational studies carried out on a rhodium precatalyst and on a conceivable intermediate in the hydrogenation catalytic cycle shed some light on the role played by hydrogen bonding, which is likely to act in a substrate-orientation effect.     

Nuclear motion effects on the density matrix of crystals: An ab initio Monte Carlo harmonic approach

In the frame of the Born-Oppenheimer approximation, nuclear motions in crystals can be simulated rather accurately using a harmonic model. In turn, the electronic first-order density matrix (DM) can be expressed as the statistically weighted average over all its determinations each resulting from an instantaneous nuclear configuration. This model has been implemented in a computational scheme which adopts an ab initio one-electron (Hartree-Fock or Kohn-Sham) Hamiltonian in the CRYSTAL program. After selecting a supercell of reasonable size and solving the corresponding vibrational problem in the harmonic approximation, a Metropolis algorithm is adopted for generating a sample of nuclear configurations which reflects their probability distribution at a given temperature. For each configuration in the sample the "instantaneous" DM is calculated, and its contribution to the observables of interest is extracted. Translational and point symmetry of the crystal as reflected in its average DM are fully exploited. The influence of zero-point and thermal motion of nuclei on such important first-order observables as x-ray structure factors and Compton profiles can thus be estimated.