Structure and dynamics of hydrated NH(4) (+): an ab initio QM/MM molecular dynamics simulation

A combined ab initio quantum mechanical/molecular mechanical (QM/MM) molecular dynamics simulation has been performed to investigate solvation structure and dynamics of NH(4) (+) in water. The most interesting region, the sphere includes an ammonium ion and its first hydration shell, was treated at the Hartree-Fock level using DZV basis set, while the rest of the system was described by classical pair potentials. On the basis of detailed QM/MM simulation results, the solvation structure of NH(4) (+) is rather flexible, in which many water molecules are cooperatively involved in the solvation shell of the ion. Of particular interest, the QM/MM results show fast translation and rotation of NH(4) (+) in water. This phenomenon has resulted from multiple coordination, which drives the NH(4) (+) to translate and rotate quite freely within its surrounding water molecules. In addition, a "structure-breaking" behavior of the NH(4) (+) is well reflected by the detailed analysis on the water exchange process and the mean residence times of water molecules surrounding the ion.     

2-[(卤代苯胺基)羰基]苯甲酸与Cu(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ)的配合物研究

本文报道了4种2-[(卤代苯胺(?))羰基]苯甲酸与Cu(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ)配合物的制备,并通过元素分析、热重分析、红外光谱和电子光谱分析以及磁化率测定对它们进行了表征.结果证明,配合物是通过羧酸根上羟基氧原子和酰胺羰基上氧原子配位成键,除Cu(Ⅱ)配合物分子为平面正方形结构外.其余均为八面体结构,只是扭曲程度不同.并对它们的配位场参数进行了计算.     

THE CORRELATION EFFECT ON THE CHAIN MOTION CONTRIBUTION TO IONIC TRANSPORT IN POLYMER ELECTROLYTES

The ionic transport process in polymer electrolytes (such as polyethylene oxide) wassimulated numerically on a two dimensional square lattice where charge carriers areaccommodated by the lattice sites connected randomly with available bonds to represent theamorphous chain configuration. Following the dynamic bond percolation theory(DBPT),the chainmotion contribution to the ionic conduction was incorporated via periodical renewal of the randombond configuration. To check and extend the prediction made by DBPT employing global abruptbond renewal,spatial correlation of the bond reassignment was introduced to the system by: 1)regional bond renewal and 2) organized bond motion. It is found that the difference between thediffusivities simulated involving regional bond renewal and those of DBPT becomes negligiblewhen the bond renewal rate approaches the carrier hopping rate.     

不可逆电极过程方波伏安法动力学研究 Ⅰ.平行催化体系

本文报道了在不可逆电极过程的强催化体系中，当采用快速方波扫描时，正、逆向电流将出现峰形。依据实验结果，提出了“迁出－进入”的等浓度面理论模型，推导了并讨论了电流方程式。结果表明，文中提出的理论能较好地说明实验结果。     

Ion Association in Lanthanide Chloride Solutions

A better understanding of the solution chemistry of the lanthanide (Ln) salts in water would have wide ranging implications in materials processing, waste management, element tracing, medicine and many more fields. This is particularly true for minerals processing, given governmental concerns about lanthanide security of supply and the drive to identify environmentally sustainable processing routes. Despite much effort, even in simple systems, the mechanisms and thermodynamics of Ln^III association with small anions remain unclear. In the present study, molecular dynamics (MD), using a newly developed force field, provide new insights into LnCl₃(aq) solutions. The force field accurately reproduces the structure and dynamics of Nd³⁺, Gd³⁺ and Er³⁺ in water when compared to calculations using density functional theory (DFT). Adaptive-bias MD simulations show that the mechanisms for ion pairing change from dissociative to associative exchange depending upon cation size. Thermodynamics of association reveal that whereas ion pairing is favourable, the equilibrium distribution of species at low concentration is dominated by weakly bound solvent-shared and solvent-separated ion pairs, rather than contact ion pairs, reconciling a number of contrasting observations of Ln^III–Cl association in the literature. In addition, we show that the thermodynamic stabilities of a range of inner sphere and outer sphere coordination complexes are comparable and that the kinetics of anion binding to cations may control solution speciation distributions beyond ion pairs. The techniques adopted in this work provide a framework with which to investigate more complex solution chemistries of cations in water.     

通过脱碳控制全球平均温度

Establishing a reliable method to predict the global mean temperature (T_e) is of great importance because CO₂ reduction activities require political and global cooperation and significant financial resources. The current climate models all seem to predict that the earth's temperature will continue to increase, mainly based on the assumption that CO₂ emissions cannot be lowered significantly in the foreseeable future. Given the earth's multifactor climate system, attributing atmospheric CO₂ as the only cause for the observed temperature anomaly is most likely an oversimplification; the presence of water (H₂O) in the atmosphere should at least be considered. As such, T_e is determined by atmospheric water content controlled by solar activity, along with anthropogenic CO₂ activities. It is possible that the anthropogenic CO₂ activities can be reduced in the future. Based on temperature measurements and thermodynamic data, a new model for predicting T_e has been developed. Using this model, past, current, and future CO₂ and H₂O data can be analyzed and the associated T_e calculated. This new, esoteric approach is more accurate than various other models, but has not been reported in the open literature. According to this model, by 2050, T_e may increase to 15.5 ℃ under "business-as-usual" emissions. By applying a reasonable green technology activity scenario, T_e may be reduced to approximately 14.2 ℃. To achieve CO₂ reductions, the scenario described herein predicts a CO₂ reduction potential of 513 gigatons in 30 years. This proposed scenario includes various CO₂ reduction activities, carbon capturing technology, mineralization, and bio-char production; the most important CO₂ reductions by 2050 are expected to be achieved mainly in the electricity, agriculture, and transportation sectors. Other more aggressive and plausible drawdown scenarios have been analyzed as well, yielding CO₂ reduction potentials of 1051 and 1747 gigatons, respectively, in 30 years, but they may reduce global food production. It is emphasized that the causes and predictions of the global warming trend should be regarded as open scientific questions because several details concerning the physical processes associated with global warming remain uncertain. For example, the role of solar activities coupled with Milankovitch cycles are not yet fully understood. In addition, other factors, such as ocean CO₂ uptake and volcanic activity, may not be negligible.     

Hypersurfaces of prescribed mean curvature enclosing a given body

Given a smooth domain Ω in ℝ ^m+1 with compact closure and a smooth integrable functionh: ℝ ^m+1→ℝ satisfyingh(x)≥H _∂Ω (x) on ∂Ω whereH _∂ω denotes the mean curvature of ∂Ω calculated w.r.t. the interior unit normal we show that there is a setA⊂ℝ ^m+1 with the properties andH _∂A=h on ∂A.     

Optimal convergence properties of kernel density estimators without differentiability conditions

Let X ₁, X ₂, ..., X _n be independent observations from an (unknown) absolutely continuous univariate distribution with density f and let % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiiYdd9qrFfea0dXdf9vqai-hEir8Ve% ea0de9qq-hbrpepeea0db9q8as0-LqLs-Jirpepeea0-as0Fb9pgea% 0lrP0xe9Fve9Fve9qapdbaqaaeGacaGaaiaabeqaamaabaabcaGcba% GabmOzayaajaGaaiikaiaadIhacaGGPaGaeyypa0Jaaiikaiaad6ga% caWGObGaaiykamaaCaaaleqabaGaeyOeI0IaaGymaaaakmaaqadaba% Gaam4saiaacUfadaWcgaqaaiaacIcacaWG4bGaeyOeI0Iaamiwamaa% BaaaleaacaWGPbaabeaakiaacMcaaeaacaWGObGaaiyxaaaaaSqaai% aadMgacqGH9aqpcaaIXaaabaGaamOBaaqdcqGHris5aaaa!5356!\[\hat f(x) = (nh)^{ - 1} \sum\nolimits_{i = 1}^n {K[{{(x - X_i )} \mathord{\left/ {\vphantom {{(x - X_i )} {h]}}} \right. \kern-\nulldelimiterspace} {h]}}} \] be a kernel estimator of f(x) at the point x, \s-<x<, with h=h _n (h _n O and nh _n , as n) the bandwidth and K a kernel function of order r. Optimal rates of convergence to zero for the bias and mean square error of such estimators have been studied and established by several authors under varying conditions on K and f. These conditions, however, have invariably included the assumption of existence of the r-th order derivative for f at the point x. It is shown in this paper that these rates of convergence remain valid without any differentiability assumptions on f at x. Instead some simple regularity conditions are imposed on the density f at the point of interest. Our methods are based on certain results in the theory of semi-groups of linear operators and the notions and relations of calculus of finite differences.This research was supported in part by grants from the Natural Sciences and Engineering Research Council of Canada and the University of Alberta Central Research Fund.     

Proof of some conjectures on the mean-value of Titchmarsh series — III

With some applications in view, the following problem is solved in some special case which is not too special. LetF(s) =Σ _n ^∞ =1a_n λ _n ^−s be a generalized Dirichlet series with 1 =λ ₁ <λ ₂ < …,λ _n≤Dn, andλ _n+1 -λ _n ≥D ^{− 1} λ _n+1 ^{− a} where α>0 andD(≥ 1) are constants. Then subject to analytic continuation and some growth conditions, a lower bound is obtained for . These results will be applied in other papers to appear later.     

Partition function zeros for the one-dimensional ordered plasma in Dirichlet boundary conditions

We consider the grand canonical partition function for the ordered one-dimensional, two-component plasma at fugacity in an applied electric fieldE with Dirichlet boundary conditions. The system has a phase transition from a low-coupling phase with equally spaced particles to a high-coupling phase with particles clustered into dipolar pairs. An exact expression for the partition function is developed. In zero applied field the zeros in the plane occupy the imaginary axis from –i to –i_c and i_c to i for some _c. They also occupy the diamond shape of four straight lines from ±i_c to _c and from ±i_c to –_c. The fugacity acts like a temperature or coupling variable. The symmetry-breaking field is the applied electric fieldE. A finite-size scaling representation for the partition in scaled coupling and scaled electric field is developed. It has standard mean field form. When the scaled coupling is real, the zeros in the scaled field lie on the imaginary axis and pinch the real scaled field axis as the scaled coupling increases. The scaled partition function considered as a function of two complex variables, scaled coupling and scaled field, has zeros on a two-dimensional surface in a domain of four real variables. A numerical discussion of some of the properties of this surface is presented.