Normal halogen dependence of 13C NMR chemical shifts of halogenomethanes revisited at the four‐component relativistic level

The ‘Normal Halogen Dependence’ of ¹³C NMR chemical shifts in the series of halogenomethanes is revisited at the four‐component relativistic level. Calculations of ¹³C NMR chemical shifts of 70 halogenomethanes have been carried out at the density functional theory (DFT) and MP2 levels with taking into account relativistic effects using the four‐component relativistic theory of Dirac‐Coulomb within the different computational methods (4RPA, 4OPW91) and hybrid computational schemes (MP2 + 4RPA, MP2 + 4OPW91). The most efficient computational protocols are derived for practical purposes. Relativistic shielding effect reaches as much as several hundreds of ppm for heavy halogenomethanes, and to account for this effect in comparison with experiment at the qualitative level, relativistic Dyall's basis sets of triple‐zeta quality or higher are to be used within the framework of the four‐component relativistic theory taking into account solvent effects. Relativistic geometrical optimization (as compared with the non‐relativistic level) is essential for the molecules containing at least two iodines at one carbon atom. Copyright © 2016 John Wiley & Sons, Ltd.     

Open‐chain unsaturated selanyl sulfides: stereochemical structure and stereochemical behavior of their 77Se–1H spin–spin coupling constants

Stereochemical structure of nine Z‐2‐(vinylsulfanyl)ethenylselanyl organyl sulfides has been investigated by means of experimental measurements and second‐order polarization propagator approach calculations of their ¹H–¹H, ¹³C–¹H, and ⁷⁷Se–¹H spin–spin coupling constants together with a theoretical conformational analysis performed at the MP2/6‐311G** level. All nine compounds were shown to adopt the preferable skewed s‐cis conformation of their terminal vinylsulfanyl group, whereas the favorable rotational conformations with respect to the internal rotations around the C–S and C–Se bonds of the internal ethenyl group are both skewed s‐trans. Stereochemical trends of ⁷⁷Se–¹H spin–spin coupling constants originating in the geometry of their coupling pathways and the selenium lone pair effect were rationalized in terms of the natural J‐coupling analysis within the framework of the natural bond orbital approach. Copyright © 2012 John Wiley & Sons, Ltd.     

Stereochemical behavior of 2 J(Se,H) and 3 J(Se,H) spin‐spin coupling constants across sp3 carbons: a theoretical scrutiny

A theoretical study of geminal and vicinal ⁷⁷Se‐¹ H coupling constants in the benchmark dimethyl and diethyl selenides has been performed at the SOPPA level followed by the NJC analysis within the NBO approach to reveal their stereochemical behavior in respect with the three main structural factors, namely, (i) the dihedral angle dependences, (ii) the bond angle dependences and (iii) the lone pair effects. It has been demonstrated that both geminal and vicinal couplings provide a unique stereospecificity in respect with the orientational lone pair effect together with the geometry of a coupling pathway, which is of prime importance for the stereochemical studies of organoselenium compounds. Copyright © 2012 John Wiley & Sons, Ltd.     

On Effective Conductivity on ℤ d Lattice

We study the effective conductivity _e for a random wire problem on the d-dimensional cubic lattice ^d , d2 in the case when random conductivities on bonds are independent identically distributed random variables. We give exact expressions for the expansion of the effective conductivity in terms of the moments of the disorder parameter up to the 5th order. In the 2D case using the duality symmetry we also derive the 6th order expansion. We compare our results with the Bruggeman approximation and show that in the 2D case it coincides with the exact solution up to the terms of 4th order but deviates from it for the higher order terms.     

The nature of the {\bar p} metastability in helium

A new interpretation of the nature of the metastable states of antiprotons in helium is proposed. The first step is the formation of an ion ( ), which shall be called “ioncule”. After its decay a neutral “atomcule” ( ) is formed which was observed in the experiments on metastable antiprotonic helium. This model explains the experiments in a natural way, in particular the quenching by atomic and molecular admixtures and the pressure dependence of quenching in pure helium. At high helium densities the ioncule creates a vacuum bubble in helium. It is shown that the annihilation of slowed-down can be suppressed at helium pressures of ∼ 10 000 bar. This revised version was published online in August 2006 with corrections to the Cover Date.     

Strongly nonlinear luminescence in oxidized porous silicon films

Partially oxidized free-standing porous silicon films show a strongly superlinear increase in photoluminescence (PL) intensity above a threshold cw excitation intensity of 10 W/cm². The PL-intensity increase can be expressed by a power law with n9 as a function of the excitation intensity. The PL-peak wavelength of this emission is slightly redshifted from that at low-excitation levels. These changes are fully reversible and reproducible, but not observed in samples on substrate. We attribute this behavior to thermal reexcitation of carriers trapped at the dangling bond states in initially nonluminescent Si nanocrystallites.     

ENHANCEMENT OF THE FAR-UV LETHALITY IN YEAST CANDIDA GUILLIERMONDII BY NEAR-UV POST-IRRADIATION

Abstract— In experiments with the non-photoreactivable yeast Candida guilliermondii , radiations at 313, 334 and 365 nm, having no effect on untreated cell populations, produced an 'enhancing' effect on the lethality of 254 nm-pretreated cells. Wavelengths in the visible region of the spectrum did not exhibit a similar effect.     

Thermodynamics of a Fermi liquid beyond the low-energy limit

We consider the nonanalytic temperature dependences of the specific heat coefficient, C(T)/T, and spin susceptibility, chi(s)(T), of 2D interacting fermions beyond the weak-coupling limit. We demonstrate within the Luttinger-Ward formalism that the leading temperature dependences of C(T)/T and chi(s)(T) are linear in T, and are described by the Fermi liquid theory. We show that these temperature dependences are universally determined by the states near the Fermi level and, for a generic interaction, are expressed via the spin and charge components of the exact backscattering amplitude of quasiparticles. We compare our theory to recent experiments on monolayers of He3.     

Supersolids versus phase separation in two-dimensional lattice bosons

We study the nature of the ground state of the two-dimensional extended boson Hubbard model on a square lattice by quantum Monte Carlo methods. We demonstrate that strong but finite on-site interaction U along with a comparable nearest-neighbor repulsion V result in a thermodynamically stable supersolid ground state for densities larger than 1/2, in contrast to fillings less than 1/2 or for very large U, where the checkerboard supersolid is unstable towards phase separation. We discuss the relevance of our results to realizations of supersolids using cold bosonic atoms in optical lattices.