Group contributions to the infinite dilution partial molar volumes of alkanes, alcohols, and glycols in polar organic solvents

Densities of binary mixtures of polar organic solvents with alcohols were measured at 25‡C. The solvents studied were N,N-dimethylformamide, dimethylsulfoxide, and formamide while alcohols were butanol, pentanol, hexanol, and 1,4-butanediol. Density measurements of hydrocarbons (from pentane to dodecane and some heptane isomers) + N,N-dimethylformamide were also performed. From these data the apparent molar volumes of alcohols and hydrocarbons as functions of concentration were calculated. The standard partial molar volumes were obtained by extrapolation to infinite dilution and are discussed in terms of group contributions.     

计量置换参数Z值分量的测定(英文)

 以计量置换吸附理论(SDT A)为基础,从理论上推导出计量吸附模型中表征溶质对固定相亲合势大小的参数βa值与流动相中强置换剂浓度的对数呈线性关系。计量置换模型中的参数n和q(n和q分别代表1摩尔溶剂化溶质被吸附时,从吸附剂表面和从溶质分子表面所释放出的溶剂的物质的量)是计量置换参数Z值的分量,是两个非常有用的参数,可以从这个定量关系中直接获得。推导出的方程用苯的衍生物进行了实验验证,获得了较满意的结果。将这种方法计算得到的分量值与SDT A与计量置换保留模型(SDT R)相结合的方法得到的分量值进行了比较。     

Three-dimensional quantum dynamics study of vibrational predissociation of HeI_2 van der Waals molecule for low vibrational excitation using the time-dependent wave packet method

Three-dimensional quantum mechanical calculations for vibrational predissociation of HeI2(B) van der Waals molecules are presented using the time-dependent wave packet technique within the golden rule approxima tion.The total and partial decay widths,lifetimes,rates and their dependence on initial vibrational states were obtained for HeI2 at low initial vibrational excited levels.Our calculations show that the calculated tota decay widths,lifetimes and rates agree well with those extrapolated from experimental data available The predicted total decay widths as a function of initial vibrational states exhibit highly nonlinear behavior.The very short propagation time (less.than 1 ps) required in the golden rule wave packet calculation is determined by the duration time of the final state inter-action between the fragments on the vibrationally deexcited adiabatic potential surface.The final state interaction between the fragments is shown to play an important role in determining the final rotational distri     

Comparison study of several numerical integration schemes used in calculations of density functional theory

Several numerical integration schemes for the evaluation of matrix elements in density functional theory calculations have been studied and compared by computational practice. The best scheme was found to be the combination of the atomic partition function proposed by Becke with the scaled generalized Gauss-Laguerre quadrature formula for radial integration suggested by Yang, which achieve the highest convergence rate to the numerical integration. With the same number of integration points, the accuracy of the calculated results by this scheme is higher by 1 to 2 orders of magnitudes than that by other schemes. The reason for achieving higher accuracy by this scheme has been proposed preliminarily.     

Nonideal mixing of 16-(9-anthroyloxy) palmitic acid and fatty acid in monolayer

The surface pressure-molecular area curve of the mixed monolayer of 16-(9-anthroyloxy) palmitic acid (16AP) and fatty acid (palmitic or stearic acids) showed various kink points which indicated the phase transitions of the monolayer. On the basis of the surface phase rule, the phase diagrams of the mixed monolayer were elucidated. The bifunctional molecule, 16AP, takes two orientations in a monolayer state, that is, horizontal and vertical ones. Horizontally oriented 16AP and vertically oriented fatty acid form a mixed monolayer but this exhibits deviation from the ideal mixing, which was interpreted in terms of the surface regular solution theory. On the other hand, the 16AP molecule in the vertical state was found to be immiscible with the fatty acid molecule in a monolayer de spite both molecules being vertical to the surface and parallel to each other. This was caused by the participation of the 9-anthroyloxy moiety of 16AP in the interaction of 16AP and fatty acid in the hydrophobic region of the monolayer.     

Phenomenology of nonlocal cellular automata

Dynamical systems with nonlocal connections have potential applications to economic and biological systems. This paper studies the dynamics of nonlocal cellular automata. In particular, all two-state, three-input nonlocal cellular automata are classified according to the dynamical behavior starting from random initial configurations and random wirings, although it is observed that sometimes a rule can have different dynamical behaviors with different wirings. The nonlocal cellular automata rule space is studied using a mean-field parametrization which is ideal for the situation of random wiring. Nonlocal cellular automata can be considered as computers carrying out computation at the level of each component. Their computational abilities are studied from the point of view of whether they contain many basic logical gates. In particular, I ask the question of whether a three-input cellular automaton rule contains the three fundamental logical gates: two-input rules AND and OR, and one-input rule NOT. A particularly interesting edge-of-chaos nonlocal cellular automaton, the rule 184, is studied in detail. It is a system of coupled selectors or multiplexers. It is also part of the Fredkin's gate—a proposed fundamental gate for conservative computations. This rule exhibits irregular fluctuations of density, large coherent structures, and long transient times.     

Heat capacities of concentrated multicomponent aqueous electrolyte solutions at various temperatures

The specific heat capacities of the aqueous multicomponent system NaCl +KCl+MgCl₂+CaCl₂ with ionic strength between 8.3 and 9.6 (resembling Dead Sea waters) were measured between 15°C and 45°C. The obtained data were fitted to an empirical equation as a function of concentration and temperature. The thermodynamic functions of the studied multicomponent system were found to be strongly influenced by changes in MgCl₂ concentrations. The application of Young's rule to such concentrated systems was checked at 25°C. The calculated (by Young's rule) specific heat capacitiesC _p and apparent molar heat capacities C_p, of these multicomponent electrolyte solutions were in reasonable agreement with the measured values (–0.008 J-g^–1-K^–1 and –2.6 J-mol^–1-K^–1, respectively).     

Structure and Electronic Properties of Fullerenes C52q+: Is C522+ an Exception to the Pentagon Adjacency Penalty Rule?

The structure, vibrational spectra and electronic properties of the neutral, singly and doubly charged C52 fullerenes were studied by means of the Hartree-Fock method and density functional theory. Different isomers were considered, in particular those with the lowest possible number (five or six) of adjacent pentagons, and an isomer with a four-atom ring. For neutral and singly charged species, the most stable isomer is that with the lowest number of adjacent pentagons, namely five. However, for C(52)2+, the most stable structure has six adjacent pentagons. This finding, which contradicts the pentagon adjacency penalty rule, is a consequence of complete filling of the HOMO pi shell and the near-perfect sphericity of the most stable isomer. The simulated vibrational spectra show important differences in the positions and intensities of the vibrations for the different isomers.     

The problem of dependent evidence

It is appropriate to use Dempster's rule for combining belief functions only if the belief functions combined are based on independent items of evidence. What can be done in the case of dependent evidence? Often the answer is to reframe the problem. Three examples are given: one from everyday experience, one from probabilistic relaxation, and one from expert systems.     

Cramer’s rule over residue class rings of Bézout domains

Cramer’s rule over residue class rings of Bézout domains is given.