An environmental pseudopotential approach to molecular interactions: Implementation in MOLPRO

We present the implementation into the MOLPRO package of a model for the interaction of a central system with its surrounding environment. The properties of a target system enclosed by a noncovalently bound environment or solvent are modeled as those of a system embedded into the effective pseudopotential arising from the exact electrostatic Coulomb potential and the approximated exchange-repulsion potential. For the latter we use the charge-density overlap model, which relates the exchange-repulsion interaction energy between two species with the overlap of their ground-state electron charge densities. The solutions of the modified Hartree-Fock equations for the target system are obtained self-consistently. This way the exchange-induction effects arising from the converged electron-charge density of the embedded system are implicitly included. Inclusion of the correlation effects is provided by the use of post-Hartree-Fock and density-functional techniques available in the MOLPRO package. The computational and conceptual advantages provided by this approach are shown in the calculation of the dipole polarizabilities of halide and chalcogenide anions in different environments.     

Gas-phase activation and reaction dynamics of chiral ion-dipole complexes

A family of enantiomerically pure oxonium ions, that is O-protonated 1-aryl-1-methoxyethanes, has been generated in the gas phase by the (CH(3))(2)Cl(+) methylation of the corresponding 1-arylethanols. Some information on their reaction dynamics was obtained from a detailed kinetic study of their inversion of configuration and dissociation. The activation parameters of the inversion reaction are found to obey two different isokinetic relationships depending upon the nature and the position of the substituents in the oxonium ions. In contrast, the activation parameters of the dissociation reaction obey a single isokinetic relationship. The inversion and dissociation rate constants do not follow simple linear free-energy relationships. This complicated kinetic picture has been rationalized in terms of different activation dynamics in gaseous CH(3)Cl, which, in turn, determine the reaction dynamics of the oxonium ion. When the predominant activation of the oxonium ion involves resonant energy exchange from the 1015 cm(-1) CH(3) rocking mode of unperturbed CH(3)Cl, the inversion reaction proceeds through the dynamically most favored TS, characterized by the unassisted C(alpha)bond;O bond elongation. When, instead, the activation of the oxonium ions requires the formation of an intimate encounter complex with CH(3)Cl, the inversion reaction takes place via the energetically most favored TS, characterized by multiple coordination of the CH(3)OH moiety with the H(alpha) and H(ortho) atoms of the benzylic residue. The activation dynamics operating in the intimate encounter complex with CH(3)Cl is also responsible for the dissociation of most selected oxonium ions.     

Iterative Algebras without Projections

We deal with iterative algebras of functions of -valued logic lacking projections, which we call algebras without projections. It is shown that a partially ordered set of algebras of functions of -valued logic, for , without projections contains an interval isomorphic to the lattice of all iterative algebras of functions of -valued logic. It is found out that every algebra without projections is contained in some maximal algebra without projections, which is the stabilizer of a semigroup of non-surjective transformations of the basic set. It is proved that the stabilizer of a semigroup of all monotone non-surjective transformations of a linearly ordered 3-element set is not a maximal algebra without projections, but the stabilizer of a semigroup of all transformations preserving an arbitrary non one-element subset of the basic set is.     

TURNING-OVER OF THE ELECTRIC DIPOLE IN A POLYMER*

The transition from the biexciton to the exciton can turn over the direction of the electric dipole of a polymericmolecule. This turning-over action combined with the photoinduced polarization reversion can be used as a switch. Theswitching speed is governed by the relaxation time of the turning-over process, which can be determined by a dynamicalsimulation.     

Mechanism Study for Thermal/Electric Field Poling of Fused Silica

On the basis of the experimental reports, the mechanism of the second-order susceptibility ⁽²⁾ for the thermal/electric field poling of fused silica is analyzed, and expressions for ⁽²⁾ are detailedly derived and numerically calculated for the first time. By comparison the theoretical value of ⁽²⁾ with the experiment results, we propose that the effective ⁽²⁾ is created via both the interaction of the intense electric field with the third-order susceptibility ⁽³⁾ and the dipole orientation. The theoretical results show that, in the differently applied voltage, the dipole orientation and ⁽³⁾ play different role in the formation of ⁽²⁾. This theory successfully explains some experiment results.     

Nuclear electric dipole moments at ion storage rings

Upper limits on the electric dipole moments (EDM) of elementary particles and atoms are presented, and their physical implications are discussed. The implications following from the neutron and atomic experiments are of comparable interest. The nuclear EDMs can be studied at ion storage rings, with the expected sensitivity much better than . This would represent a serious progress in studies of the CP-violation problem. This revised version was published online in August 2006 with corrections to the Cover Date.     

圆截面弹性螺旋杆的稳定性与振动

基于Kirchhoff理论讨论圆截面弹性螺旋杆的动力学问题.以杆中心线的Frenet坐标系为参考系，建立用欧拉角描述的弹性杆动力学方程.讨论其在端部轴向力和扭矩作用下保持的无扭转螺旋线平衡状态.在静力学和动力学领域内讨论其平衡稳定性问题.还讨论了弹性杆平衡的Lyapunov稳定性和欧拉稳定性两种不同稳定性概念之间的区别和联系.在一次近似意义下证明了螺旋杆在空间域内的欧拉稳定性条件是时域内Lyapunov稳定性的必要条件.导出了解析形式螺旋杆三维弯曲振动的固有频率，为螺旋线倾角和受扰挠性线波数的函数. 关键词： 弹性螺旋杆 Kirchhoff动力学比拟 Lyapunov稳定性 欧拉稳定性     

垂直电偶极子在球外侧电磁场的闭合解及验证

给出了理想导体球外侧垂直电偶极子激励电场的闭合解，解决了直接场的级数表达式的不连续性问题.同球外电磁场直接级数求和表达式的计算结果进行了比较.在相同的电磁模型下，利用闭合解对一种近似方法进行了验证：当垂直电偶极子以及场点在球体表面附近并且频率较低时，这两种方法的计算结果非常一致；当垂直电偶极子以及场点不在球体表面附近并且频率较高时，闭合解的计算结果逐渐出现了近似方法未出现的干涉现象.     

Line intensities in the 1.5-μm spectral region of acetylene

Line intensities are measured for 546 transitions belonging to 13 bands of the main isotopologue ¹²C₂H₂ of the acetylene molecule, in the 1.5-μm spectral domain. A multispectrum fitting procedure is used to retrieve line parameters from Fourier transform spectra. Prior to this work, line intensities were known for only 4 bands in this spectral region, from the work of El Hachtouki and Vander Auwera [Absolute line intensities in acetylene: the 1.5 μm region. J Mol Spectrosc 2002;216:355-62]. An excellent agreement is found with the results of these authors, showing that the accuracy of both results is likely better than 1% for the strong bands. However, the spectrum becomes very crowded when one wants to study weaker bands, so that the average accuracy of the intensities reported in the present work is 5%. From these data, vibrational transition dipole moments squared and Herman-Wallis coefficients have been determined for all the bands.     

Structure–reactivity relationships of alkyl α‐hydroxymethacrylate derivatives

A series of alkyl α‐hydroxymethacrylate derivatives with various secondary functionalities (ether, ester, carbonate, and carbamate) and terminal groups (alkyl, cyano, oxetane, cyclic carbonate, phenyl and morpholine) were synthesized to investigate the effect of intermolecular interactions, H‐bonding, π–π interactions, and dipole moment on monomer reactivity. All of the monomers except one ester and one ether derivative are novel. The polymerization rates, determined by using photo‐DSC, showed the average trend (aromatic carbamate > hydroxyl > ester > carbonate ～ aliphatic carbamate ～ ether), with several exceptions due to the differences in terminal groups. There is a correlation between the chemical shift differences of the double bond carbons, the calculated dipole moments, and the reactivities only for nonhydrogen bonded monomers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011