MP2 calculation of 77Se NMR chemical shifts taking into account relativistic corrections

The main factors affecting the accuracy and computational cost of the Second‐order Möller‐Plesset perturbation theory (MP2) calculation of ⁷⁷Se NMR chemical shifts (methods and basis sets, relativistic corrections, and solvent effects) are addressed with a special emphasis on relativistic effects. For the latter, paramagnetic contribution (390–466 ppm) dominates over diamagnetic term (192–198 ppm) resulting in a total shielding relativistic correction of about 230–260 ppm (some 15% of the total values of selenium absolute shielding constants). Diamagnetic term is practically constant, while paramagnetic contribution spans over 70–80 ppm. In the ⁷⁷Se NMR chemical shifts scale, relativistic corrections are about 20–30 ppm (some 5% of the total values of selenium chemical shifts). Solvent effects evaluated within the polarizable continuum solvation model are of the same order of magnitude as relativistic corrections (about 5%). For the practical calculations of ⁷⁷Se NMR chemical shifts of the medium‐sized organoselenium compounds, the most efficient computational protocols employing relativistic Dyall's basis sets and taking into account relativistic and solvent corrections are suggested. The best result is characterized by a mean absolute error of 17 ppm for the span of ⁷⁷Se NMR chemical shifts reaching 2500 ppm resulting in a mean absolute percentage error of 0.7%. Copyright © 2015 John Wiley & Sons, Ltd.     

Nonempirical calculations of the one‐bond 29Si–13C spin–spin coupling constants taking into account relativistic and solvent corrections

The computational study of the one‐bond ²⁹Si–¹³C spin–spin coupling constants has been performed at the second‐order polarization propagator approximation (SOPPA) level in the series of 60 diverse silanes with a special focus on the main factors affecting the accuracy of the calculation including the level of theory, the quality of the basis set, and the contribution of solvent and relativistic effects. Among three SOPPA‐based methods, SOPPA(MP2), SOPPA(CC2), and SOPPA(CCSD), the best result was achieved with SOPPA(CCSD) when used in combination with Sauer's basis set aug‐cc‐pVTZ‐J characterized by the mean absolute error of calculated coupling constants against the experiment of ca 2 Hz in the range of ca 200 Hz. The SOPPA(CCSD)/aug‐cc‐pVTZ‐J method is recommended as the most accurate and effective computational scheme for the calculation of ¹J(Si,C). The slightly less accurate but essentially more economical SOPPA(MP2)/aug‐cc‐pVTZ‐J and/or SOPPA(CC2)/aug‐cc‐pVTZ‐J methods are recommended for larger molecular systems. It was shown that solvent and relativistic corrections do not play a major role in the computation of the total values of ¹J(Si,C); however, taking them into account noticeably improves agreement with the experiment. The rovibrational corrections are estimated to be of about 1 Hz or 1–1.5% of the total value of ¹J(Si,C). Copyright © 2014 John Wiley & Sons, Ltd.     

EFFECT OF COMPOSITION AND PROCESSING CONDITION ON MICROSTRUCTURAL PROPERTIES AND DURABILITY OF FLUOROPOLYMER/ACRYLIC BLENDS

Fluoropolymer blends have been widely used as binders for exterior coatings because of their excellent resistance to ultra-violet (UV) radiation as well as to many corrosive chemical agents.It is known that the fluorinated component usually has a lower glass transition temperature and easily crystallizes in the final structure depending upon the blend composition and sample annealing condition.We investigated the effect of blend composition and annealing process (slow and fast cooling) on the surface mor...     

Experimental exposure of nuclear emulsion by xenon nuclei at the JINR nuclotron

Nuclear emulsion was exposed to xenon nuclei accelerated at the JINR Nuclotron. Visual and automated scanning of the extracted beam profile was performed using the exposed emulsion film.     

Luminescent sol–gel materials based on lanthanide aminopolycarboxylates (Ln = Nd, Eu, Tb, Yb)

Luminescent organic–inorganic hybrid materials containing immobilized lanthanide(III) complexes (Ln = Nd, Eu, Tb, Yb) with modified ethylenediaminetetraacetic and diethylenetriaminepentaacetic acid were synthesized by sol–gel method. Obtained hybrids exhibit 4f-luminescence in the visible (Eu(III) and Tb(III)) and IR-region (Nd(III) and Yb(III)). The influence of the hybrid matrix on the lanthanide luminescence was established and it was shown, that the location of resonance level of Eu(III) is optimal for efficient energy transfer from matrix, while in the case of Tb(III) energy transfer does not occur and Tb(III) is able to absorb energy only due to its own week f–f transitions. It was also established that the inorganic matrix leads to elimination of nonradiative energy losses and increase of 4f-luminescence lifetimes. Covalent binding of Ln(III) aminopolycarboxylates in the matrix allows to consider obtained materials as promising for creation of photo- and chemically-stable luminescent sensors.     

Complex domain structure in a magnetic film with oblique anisotropy

Analytical formulas have been derived to calculate the distortion of the stripe domain structure in a ferromagnetic film under the action of a bubble domain formed in this film. On the basis of the formulas obtained, an experimentally obtained domain configuration has been calculated. The results of the calculation coincide with the observation data within the experimental error.     

Design and study of a high-current 5-cell superconducting rf cavity

The Advanced Photon Source （APS） at Argonne National Laboratory is considering the development of a superconducting linac-based fourth-generation hard X-ray source to meet future scientific needs of the hard X-ray user community. This work specifically focuses on the design of an optimized 5-cell superconducting radio-frequency structure well suited for a high-energy, high-beam-current energy recovery linac. The cavity design parameters are based on the APS storage ring nominal 7 GeV and 100 mA beam operation. A high-current 5-cell cw superconducting cavity operating at 1.4 GHz has been designed. In order to achieve a high current, the accelerating cavity shape has been optimized and large end-cell beam pipes have been adopted. The beam break-up threshold of the cavity has been estimated using the code TDBBU, which predicts a high threshold beam current for a 7 GeV energy recovery linac model. A copper prototype cavity has been fabricated that uses half-cell modules, initially assembled by clamping the cells together.     

Relativistic alpha-particles from inelastic collisions of nuclei of24Mg in photoemulsion at 4.5 GeV/(c· nucleon)

The transverse momentum spectra and correlation characteristics of secondary -particles (fragments of the²⁴Mg nuclei) are studied. An excessive number of high-momentum -particles are found, which cannot be explained by the statistical model. It is shown that the azimuth correlations of -particles can be due to a large transverse momentum of the fragmenting residual magnesium nucleus.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 19–23, May, 1991.     

非导电型各向同性手性介质中非线性旋光的宏观理论

采用经典电磁场理论描述非导电型各向同性手性介质,研究了圆偏振抽运光作用下线偏振信号光的非线性旋光现象．给出了非线性旋光角的解析表达式．用该公式计算的结果与实验结果一致. 关键词：     

Luminescence of Ytterbium in Complexes with Cryptands Containing Bipyridine and Biisoquinoline Fragments

Some characteristics of 4fluminescence of an ytterbium ion with cryptands containing bipyridine and biisoquinoline fragments have been studied for the first time. The relationship has been established between the changes in these characteristics and the structure of a macrocyclic ligand in H₂O and D₂O at 295 and 77 K. It is shown that the highest intensities and lifetimes of 4fluminescence are observed in those complexes where a lanthanide ion is most effectively protected against water molecules.