Isomers of C20: an energy profile III

Semiempirical calculations, at the PM3 level provided within the Winmopac v2.0 software package, are used to geometrically optimize and determine the absolute energies (heats of formation) of a variety of C(20) isomers that are predicted to exist in and around the ring and cage isomers. Using the optimized Cartesian coordinates for the ring and the cage isomers, a saddle-point calculation was performed. The resulting energy profile, consisting of a series of peaks and valleys, is used as a starting point for the identification and location of fifteen additional isomers of C(20) that are predicted to be energetically stable, both via geometry optimizations and force constant analysis. These additional isomers were subsequently determined to lie adjacent to one another on the potential surface and establish a step-wise transformation between the ring and the cage. Transition-state optimization of the Cartesian coordinates at the saddle point between adjacent isomers was performed to quantify the energy of the transition state. The step-wise process from one isomer to another, which extends out over the three-dimensional surface, is predicted to require approximately 15% less energy than that of the direct, two-dimensional transformation predicted in the bowl-cage profile. However, the net atomic rearrangement for the step-wise process is about four times greater than that of the direct process. Although less in energy, the amount of atomic rearrangement in the step-wise process would make the occurrence of such a route prohibitive. Utilizing the direct distance separating the three primary isomers (ring, bowl, cage), the method of triangulation is performed to quantitatively position other C(20) structures on the potential surface, relative to the ring, bowl, and cage isomers.     

N-取代吩噻嗪和DDQ的电荷转移络合作用

具有盼嘤酸化学结构的化合物有广泛的用途I‘－＼其中吩嘤埃衍生物在医学上用作抗精神病药物特别受到药理学家们的注意，发现其药理作用与其分子提供电子的能力有关卜‘」但是我们应该注意到，作为抗精神病药物的吩嚷嚷衍生物，其吩座爆分子的氮原子都连有一个叔胺基链问，例如氯丙障（I）和奋乃静（11）．而我们知道，胺类特别是叔胺类有强的提供电子的能力＊；在上述的药物分子中是主要的提供电子因素，因此以这类化合物作为给体研究其供电子能力，是不能实际反映吩嘤嗓分子本身的给电子能力的．吩嘤噪类属于二苯并杂环化合物，分子中既…     

Inter- and intramolecular potential for the N-formylglycinamide-water system. A comparison between theoretical modeling and empirical force fields

An intramolecular NEMO potential is presented for the N-formylglycinamide molecule together with an intermolecular potential for the N-formylglycinamide-water system. The intramolecular N-formylglycinamide potential can be used as a building block for the backbone of polypeptides and proteins. Two intramolecular minima have been obtained. One, denoted as C5, is stabilized by a hydrogen bonded five member ring, and the other, denoted as C7, corresponds to a seven membered ring. The interaction between one water molecule and the N-formylglycinamide system is also studied and compared with Hartree-Fock SCF calculations and with the results obtained for some of the more commonly used force fields. The agreement between the NEMO and SCF energies for the complexes is in general superior to that of the other force fields. In the C7 region the surfaces obtained from the intramolecular part of the commonly used force fields are too flat compared to the NEMO potential and the ab initio calculations. We further analyze the possibility of using a charge distribution obtained from one conformation to describe the charge distribution of other conformations. We have found that the use of polarizabilities and generic dipoles can model most of the changes in charge density due to the different geometry of the new conformations, but that one can expect additional errors in the interaction energies that are of the order of 1 kcal/mol.     

结合三维静电势参数研究二取代苯的定量结构－疏水性关系

对含有常见取代基的92个二取代苯化合物进行了结构优化和静电势及其导出参数的计算,运用多元线性回归方法对化合物的疏水常数与分子的结构参数进行了关联.结果表明,分子表面负静电势的加和ΣV－S、分子空间内最负的静电势Vmin、表面最大静电势Vs,max以及分子体积V、极性表面积APS和分子的偶极密度μ/V这六个参数,可以很好地用于表达这些化合物疏水性与分子结构间的定量关系,而不用具体考虑分子中极性基团间的相互作用.用建立起来的QSPR(quantitative structure-property relationship)关系式对111个类似化合物的疏水性进行了预测,获得了满意的结果.     

Transients of the Open-Circuit Potential Observed during the Interaction of Formic Acid with Preliminarily Adsorbed Oxygen on a Platinized Platinum Electrode

Transients of the open-circuit potential, which are observed during the interaction of formic acid with preliminarily adsorbed oxygen (O_ads) on a Pt/Pt electrode in 0.5 M H₂SO₄, are measured. It is established, by means of the method of cathodic potentiodynamic pulses, that the slowest interaction of formic acid with O_ads occurs in the region of large coverages of the electrode surface by oxygen (θ_O ∼1–0.8). A presumption is put forward that the process rate in this region is defined by a direct reaction of O_ads with molecules of formic acid from the bulk solution. It is shown that the interaction of formic acid with O_ads in the region of intermediate coverages (θ_O ∼ 0.8–0.2) proceeds via a mechanism of “conjugated reactions.” Transients of the open-circuit potential for formic acid are compared to transients for carbon monoxide obtained in analogous conditions. The substantially shorter overall time of potential decay in the case of CO (at the same concentrations) is caused by a faster reaction of CO with adsorbed oxygen in the region of large θ_O. The difference is explained by assuming that the HCOOH adsorption as opposed to CO bears a dissociative character.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 936–942.Original Russian Text Copyright © 2005 by Manzhos, Maksimov, Podlovchenko.     

Fitting complex potential energy surfaces to simple model potentials: application of the simplex-annealing method

A stochastic method of optimization, which combines simulated annealing with simplex, is implemented to fit the parameters of a simple model potential. The main characteristic of the method is that it explores the whole space of the parameters of the model potential, and therefore it is very efficient in locating the global minimum of the cost function, in addition to being independent of the initial guess of the parameters. The method is employed to fit the complex intermolecular potential energy surface of the dimer of water, using as a reference the spectroscopic quality anisotropic site-site potential of Feller et al. The simple model potential chosen for its reparameterization is the MCY model potential of Clementi et al. The quality of the fit is assessed by comparing the geometry of the minimum, the harmonic frequencies, and the second virial coefficients of the parameterized potential with the reference one. Finally, to prove more rigorously the robustness of this method, it is compared with standard nonstochastic methods of optimization.     

Schrödinger Equation Solutions for the Central Field Power Potential Energy I. V(r) = V 0(r/a 0)2ν−2, ν ≥ 1

The solution of a generalized non-relativistic Schrödinger equation with radial potential energy V(r)=V ₀(r/a ₀)^2–2 is presented. After reviewing the general properties of the radial ordinary differential equation, power series solutions are developed. The Green's function is constructed, its trace and the trace of its first iteration are calculated, and the ability of the traces to provide upper and lower bounds for the ground eigenvalue is examined. In addition, WKB-like solutions for the eigenvalues and eigenfunctions are derived. The approximation method yields valid eigenvalues for large quantum numbers (Rydberg states).     

固定HCG抗体膜的跨膜电位

高分子膜作为一项新兴技术,在很多领域得到日益广泛的应用.近十几年,随着生物工程和生物传感器的迅速发展,高分子生物功能膜的研究倍受重视.高分子生物功能膜是采用固定化技术,将具有分子识别功能的材料(如酶、抗原、抗体等)固定在高分子膜上而制得的.在固定化膜表面发生的生物化学反应,可以引起膜的荷电状态的变化,从而导致跨膜电位的变化。有关固定化膜的报导较多,但主要限于固定化的方法及其应用方面的研究,而有关高分     

Comparison of the effective core potential and model potential methods in studies of electron correlation energy in molecules: Dihalides and halogen hydrides

Summary The effective core potential and model potential methods were used in post-SCF calculations on HC1, HBr, Cl₂, and Br₂ in order to gain insight into the effect of insufficient representation of inner nodes in the valence orbitals of the approximate methods. The results show that while the correlation energy may be slightly overestimated (by 1–7%), both the electric moment functions and the quantities depending on energy differences are consistently similar for the methods studied and close to the results from all-electron calculations.Dedicated to Prof. Klaus Ruedenberg