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51.
Ricardo L. Mancera Michalis Chalaris Jannis Samios 《Journal of Molecular Liquids》2004,110(1-3):147-153
We have carried out a molecular dynamics study of dimethyl sulfoxide (DMSO) in water at 298 K at two different densities by simulating two different concentrations: 0.055 and 0.19 mole fraction. We have found an enhancement in the structure of water, an effect that becomes more pronounced as the concentration of DMSO increases. At both concentrations there is a well-defined hydration structure around the oxygen atom of DMSO, which is able to establish strong hydrogen bonds with surrounding water molecules. An increase in the concentration of DMSO depletes the solution of bulk water molecules, reducing the number of hydrogen bonds that water can have in the immediate vicinity of DMSO but increasing the strength of the hydrogen bonds made between the oxygen atom of DMSO and water. There is clear evidence of ‘hydrophobic’ hydration around the methyl groups of DMSO, which is enhanced as the concentration of DMSO increases. 相似文献
52.
We extend an earlier method for solving kinetic boundary layer problems to the case of particles moving in aspatially inhomogeneous background. The method is developed for a gas mixture containing a supersaturated vapor and a light carrier gas from which a small droplet condenses. The release of heat of condensation causes a temperature difference between droplet and gas in the quasistationary state; the kinetic equation describing the vapor is the stationary Klein-Kramers equation for Brownian particles diffusing in a temperature gradient. By means of an expansion in Burnett functions, this equation is transformed into a set of coupled algebrodifferential equations. By numerical integration we construct fundamental solutions of this equation that are subsequently combined linearly to fulfill appropriate mesoscopic boundary conditions for particles leaving the droplet surface. In view of the intrinsic numerical instability of the system of equations, a novel procedure is developed to remove the admixture of fast growing solutions to the solutions of interest. The procedure is tested for a few model problems and then applied to a slightly simplified condensation problem with parameters corresponding to the condensation of mercury in a background of neon. The effects of thermal gradients and thermodiffusion on the growth rate of the droplet are small (of the order of 1%), but well outside of the margin of error of the method. 相似文献
53.
The potential of the internal rotation of the methyl group was determined for o-, m-, and p-fluorotoluene cations by pulsed field ionization spectroscopy. The potential of the internal rotational motion was also surveyed for other toluene derivative cations. It was found that the barrier height generally increases by ionization. The increase in the barrier height has been discussed in connection with the reduction of the internal rotational constant B by ionization. The geometrical distortion of the methyl group during the internal rotation has been suggested. 相似文献
54.
Solomon Fekade Mulugeta Bekele 《The European Physical Journal B - Condensed Matter and Complex Systems》2002,26(3):369-374
We analyze the relaxation behavior of a bistable system when the background temperature profile is inhomogeneous due to the
presence of a localized hot region (blowtorch) on one side of the potential barrier. Since the diffusion equation for inhomogeneous
medium is model-dependent, we consider two physical models to study the kinetics of such system. Using a conventional stochastic
method, we obtain the escape and equilibration rates of the system for the two physical models. For both models, we find that
the hot region enhances the escape rate from the well where it is placed while it retards the escape rate from the other well. However, the value of the escape rate from the well where the hot region is placed differs
for the two models while that of the escape rate from the other well is identical for both. This work, for the first time,
gives a detailed report of the similarities and differences of the escape rates and, hence, exposes the common and distinct
features of the two known physical models in determining the way the bistable system relaxes.
Received 25 September 2001 相似文献
55.
尹传存 《数学物理学报(A辑)》1997,17(2):145-151
设中的角域.该文绘出了A上正调和函数的Martin表示,讨论了极小调和函数与条件Brown运动的一个0—1律之间的关系,并给出了A上极小调和函数的表现形式, 相似文献
56.
In a previous paper we gave a new formulation and derived the Euler equations and other necessary conditions to solve strong, pathwise, stochastic variational problems with trajectories driven by Brownian motion. Thus, unlike current methods which minimize the control over deterministic functionals (the expected value), we find the control which gives the critical point solution of random functionals of a Brownian path and then, if we choose, find the expected value.This increase in information is balanced by the fact that our methods are anticipative while current methods are not. However, our methods are more directly connected to the theory and meaningful examples of deterministic variational theory and provide better means of solution for free and constrained problems. In addition, examples indicate that there are methods to obtain nonanticipative solutions from our equations although the anticipative optimal cost function has smaller expected value.In this paper we give new, efficient numerical methods to find the solution of these problems in the quadratic case. Of interest is that our numerical solution has a maximal, a priori, pointwise error of O(h3/2) where h is the node size. We believe our results are unique for any theory of stochastic control and that our methods of proof involve new and sophisticated ideas for strong solutions which extend previous deterministic results by the first author where the error was O(h2).We note that, although our solutions are given in terms of stochastic differential equations, we are not using the now standard numerical methods for stochastic differential equations. Instead we find an approximation to the critical point solution of the variational problem using relations derived from setting to zero the directional derivative of the cost functional in the direction of simple test functions.Our results are even more significant than they first appear because we can reformulate stochastic control problems or constrained calculus of variations problems in the unconstrained, stochastic calculus of variations formulation of this paper. This will allow us to find efficient and accurate numerical solutions for general constrained, stochastic optimization problems. This is not yet being done, even in the deterministic case, except by the first author. 相似文献
57.
Jerzy Cioslowski 《Theoretical chemistry accounts》1992,81(4-5):319-327
Summary A new index, called the differential density matrix overlap (DDMO), is proposed for assessment of the electron correlation effects in atoms and molecules. DDMO can be easily calculated as the negative value of the correlation energy derivative with respect to the relative position of the occupied and virtual orbitals. DDMO is transparent to physical interpretation. It can serve as a tool for analyzing the accuracy of approximate electron correlation methods and the validity of the Hartree-Fock wavefunction as the zeroth-order approximation. The properties of DDMO are discussed using test calculations on 11 atoms and molecules as an example. 相似文献
58.
59.
M.C. Ubaldi V. Stasi U. Colombo D. Piccinin M. Martinelli 《Photonics and Nanostructures》2007,5(2-3):145-148
Roughness reduction of a submicron waveguide profile in chemically amplified negative resist is here performed by proper selection of an alkali-based developer, taking into account that its smaller molecules lead to smoother resist surface by altering the developing mechanism of aggregate extraction performed with standard quaternary ammonium hydroxide. Roughness is then analyzed by means of classical Atomic Force Microscope inspection; furthermore, a non-invasive line edge roughness analysis approach based on top-down scanning electron microscope acquisition gives comparable results, in terms of standard deviation and molecular aggregate periodicity. 相似文献
60.
In this paper, nonlinear systems having multiple equilibrium points and low order dynamics are investigated. Roll motions of ships are studied by means of modern nonlinear techniques to exemplify the behavior of such nonlinear systems in the case when they are under the influence of external sinusoidal disturbances with unknown amplitudes. The main objective is to analyze the performance of this system at different operating conditions, including those giving rise to chaos, and to design a controller with an overparameterized structure to stabilize the system at the origin. A nonlinear recursive backstepping controller is proposed and the transient performance is investigated. Lyapunov-based techniques are used to force systematic following of a reference model while introducing a nonlinear parameter estimator to guarantee adaptivity. Robustness problems as well as ways to tune the controller parameters are examined. Simulation results are submitted for the uncontrolled and controlled cases, verifying the effectiveness of the proposed controller. Finally, a discussion and conclusions are given with possible future extensions. 相似文献