Ab initio calculations of accurate dissociation energy and analytic potential energy function for the second excited state B1∏ of 7LiH

The reasonable dissociation limit of the second excited singlet state B¹∏ of ⁷LiH molecule is obtained. The accurate dissociation energy and equilibrium geometry of the B¹\Pi state are calculated using a symmetry-adapted-cluster configuration--interaction method in full active space. The whole potential energy curve for the B¹∏ state is obtained over the internuclear distance ranging from about 0.10nm to 0.54nm, and has a least-square fit to the analytic Murrell--Sorbie function form. The vertical excitation energy is calculated from the ground state to the B¹∏ state and compared with previous theoretical results. The equilibrium internuclear distance obtained by geometry optimization is found to be quite different from that obtained by single-point energy scanning under the same calculation condition. Based on the analytic potential energy function, the harmonic frequency value of the B¹∏ state is estimated. A comparison of the theoretical calculations of dissociation energies, equilibrium interatomic distances and the analytic potential energy function with those obtained by previous theoretical results clearly shows that the present work is more comprehensive and in better agreement with experiments than previous theories, thus it is an improvement on previous theories.     

Two-Dimensional Coulomb Systems on a Surface of Constant Negative Curvature

We study the equilibrium statistical mechanics of classical two-dimensional Coulomb systems living on a pseudosphere (an infinite surface of constant negative curvature). The Coulomb potential created by one point charge exists and goes to zero at infinity. The pressure can be expanded as a series in integer powers of the density (the virial expansion). The correlation functions have a thermodynamic limit, and remarkably that limit is the same one for the Coulomb interaction and some other interaction law. However, special care is needed for defining a thermodynamic limit of the free energy density. There are sum rules expressing the property of perfect screening. These generic properties can be checked on the Debye–Hückel approximation, and on two exactly solvable models, the one-component plasma and the two-component plasma, at some special temperature.     

Polyethylene compounds with antimicrobial surface properties

The present study aims at antimicrobial polyethylene surfaces. To achieve this, LLDPE was compounded with the polymeric biocide poly(2-tert-butylaminoethyl) methacrylate TBAM (bulk modification with 1.5-5.0 wt.% of TBAM). Surfaces of these polymer compounds were then subjected to microbial assays. Using standard methods the colony forming units (CFU) for Escherichia coli and Staphylococcus aureus were determined on these surfaces. In all cases, polyethylene surfaces with highly antimicrobial properties were achieved. An average reduction of 10⁴ CFU ml⁻¹ compared to neat LLDPE was achieved. The surfaces of these LLDPE/TBAM compounds were assessed by electrokinetic (zeta potential) measurements. The results indicate a relation between the antimicrobial activity and the zeta-potential of the polymer compounds. Moreover, the antimicrobial compounds were investigated towards biofilm formation. Compared to pristine LLDPE, the surfaces of the polymer compounds showed less adhering biofilm after a testing period of 16 weeks.     

A Monte Carlo method for an objective Bayesian procedure

This paper describes a method for an objective selection of the optimal prior distribution, or for adjusting its hyper-parameter, among the competing priors for a variety of Bayesian models. In order to implement this method, the integration of very high dimensional functions is required to get the normalizing constants of the posterior and even of the prior distribution. The logarithm of the high dimensional integral is reduced to the one-dimensional integration of a cerain function with respect to the scalar parameter over the range of the unit interval. Having decided the prior, the Bayes estimate or the posterior mean is used mainly here in addition to the posterior mode. All of these are based on the simulation of Gibbs distributions such as Metropolis' Monte Carlo algorithm. The improvement of the integration's accuracy is substantial in comparison with the conventional crude Monte Carlo integration. In the present method, we have essentially no practical restrictions in modeling the prior and the likelihood. Illustrative artificial data of the lattice system are given to show the practicability of the present procedure.     

Intrinsic field theory of chemical reactions

An intrinsic principle of least action is presented for the intrinsic dynamism of chemical reactions. Then, as the stationary trajectory, a meta-IRC (intrinsic reaction coordinate) draws a geodesic curve in a rigged Riemannian space. This establishes a geodesic law for the intrinsic dynamism. Moreover, a diagrammatic perturbation theory is formulated for the intrinsic dynamism, and a dynamical interaction between a chemically reacting system and a background system is investigated. Then, the structural stability of the system is discussed using a new concept of the dynamical potential field. An example is given in order to elucidate the present theory.Dedicated to Prof. Hermann Hartmann on the occasion of his 65th birthday.     

Determination of the correlation effects in molecules using the complete error potential

Summary The complete error potential is used for the study of the correlation of molecules. The correlation can be seen as a relaxation of the electrons and a relaxation of the nuclei. From the Fermi sea, the electronic relaxation gives rise to a partial excitation of each orbital which collectively generates a linear, a surface or a volume pressure; the resulting forces acting on the nuclei are defined in a general theory of the intramolecular forces. H₃, H ₃ ⁺ , the diatoms and the hydrid of the first nine elements are taken as examples.     

Electrical Potential Distribution around a Charged Colloidal Particle: Nonlinear Integral Equation

多电解质溶液中带电胶体粒子的电势分布由球形Ｐｏｉｓｓｏｎ－Ｂｏｌｔｚｍａｎｎ方程（ＰＢＥ）描述．ＰＢＥ是一个非线性的微分方程，且难以求得其解析解．本文采用非线性Ｐ－Ｂ积分方程，计算电势分布的数值解．首先，根据静电场和热力学系统中的物理定理，导出描述电势分布的Ｐ－Ｂ积分方程（ＰＢＩＥ）；其次，用迭代方法求ＰＢＩＥ的数值解．最后，计算了在３－１型电解液中无量纲半径κａ分别为０．１２和０．２２，无量纲表面电势ξ分别为１，２，４，６时球形胶体粒子外部的电势值．为了检验数值解的精度，计算了表面电荷密度，并与Ｌｏｅｂ（１９６１）和Ｏｓｈｉｍａ（１９９５）等人的结果比较，本文结果的相对误差小于１％，优于Ｏｓｈｉｍａ的结果．     

Electrochiroptical systems based on biphenyl-2,2′-diyl-type dicationic dyes: strong chiroptical signals through the transmission of point chirality to axial chirality

Huge CD amplitude (A = +538) was attained by diastereomeric preference (50% de) for the title dication with two bis[4-(R)-sec-butoxyphenyl]methylium units in benzene at 23 °C. Intramolecular π-π stacking is the origin for effective transmission of point chirality to axial chirality to attain the chiroptical enhancement of 400-times. Thanks to the strong CD signaling, chiroptical changes upon electrolysis could be readily detected, thus realizing a new class of electrochiroptical response systems. Chiroptical properties could also be modified by solvent polarity.     

分子筛修饰电极的研究（Ⅰ）──氢醌／醌电对在分子筛修饰电极上的电化学行为

考察了中性分子电对Ｈ_２Ｑ／Ｑ在１３Ｘ型分子筛修饰电极上的电化学行为。发现Ｈ_２Ｑ／Ｑ电对在修饰电极上电响应迅速，为双电子可逆反应，不受溶液温度及电极与溶液相对运动的影响，而与溶液的ｐＨ值有关。当ｐＨ≤２．０时，修饰电极对Ｈ_２Ｑ／Ｑ电对的氧化／还原有明显的催化作用．     

Ab initio study of the complexes of halogen-containing molecules RX (X=Cl, Br, and I) and NH3: towards understanding the nature of halogen bonding and the electron-accepting propensities of covalently bonded halogen atoms

Ab initio calculations have been performed on a series of complexes formed between halogen-containing molecules and ammonia to gain a deeper insight into the nature of halogen bonding. It appears that the dihalogen molecules form the strongest halogen-bonded complexes with ammonia, followed by HOX; the charge-transfer-type contribution has been demonstrated to dominate the halogen bonding in these complexes. For the complexes involving carbon-bound halogen molecules, our calculations clearly indicate that electrostatic interactions are mainly responsible for their binding energies. Whereas the halogen-bond strength is significantly enhanced by progressive fluorine substitution, the substitution of a hydrogen atom by a methyl group in the CH(3)X...NH(3) complex weakened the halogen bonding. Moreover, remote substituent effects have also been noted in the complexes of halobenzenes with different para substituents. The influence of the hybridization state of the carbon atom bonded to the halogen atom has also been examined and the results reveal that halogen-bond strengths decrease in the order HC triple bond CX > H(2)C=CHX approximately O=CHX approximately C(6)H(5)X > CH(3)X. In addition, several excellent linear correlations have been established between the interaction energies and both the amount of charge transfer and the electrostatic potentials corresponding to an electron density of 0.002 au along the R-X axis; these correlations provide good models with which to evaluate the electron-accepting abilities of the covalently bonded halogen atoms. Finally, some positively charged halogen-bonded systems have been investigated and the effect of the charge has been discussed.