Electrostatic lattice coefficients and binding energy of orthorhombic La2-x Sr x CuO4

Three valency models for orthorhombic La_2-x Sr _x CuO₄ were investigated for increasing Sr concentrationsx (0x0.21): 1. Cu²⁺Cu³⁺, 2. apex O^2–O^– and 3. in-plane O^2–O^–. All calculations were done by using structural parameters valid for the temperature range from 10 to 22 K. We thereby calculated the electrostatic interaction energy which, next to ionization potentials and electron affinities, comprises a major of the binding energyE _B of crystals. Second-order effects were accounted for by calculating the strength of ionic dipole moments induced by crystal electric fields at relevant lattice sites. Their largest strengths are comparable to the dipole moment of the water molecule. Three out of five dipoles in La_2-x Sr _x CuO₄ vanish during the transition from the orthorhombic to the tetragonal phase. The binding energy differences between the different models suggest that the system is in a state of model 1. However, the differences are very small, being in the order of 0.3 to 0.76 eV atx=0.13.     

The Green relations approach to congruences on completely regular semigroups

On the congruence lattice (2(5) of a completely regular semigroup S the following mappings are considered _p: P and _p: VP, whereP is any of the Green relationsH, L, R orD. The equivalence relationsP andP ^V induced by these maps represent the main object of study in the paper. The former is a complete -congruence whereas the latter is a complete congruence onC(S). In particularH ,H ^V,L ^V,R ^V coincide with the kernel, trace, left trace and right trace relations onC(S), respectively. All essential properties known for the latter relations carry over to the new relationsP andP ^V. In addition, some interesting interplays of these provide for more richness in the theory of congruences on completely regular than is the case for the kernel-trace approach to congruences on regular semigroups.     

Homogenization of the heat equation for a domain with a network of pipes with a well-mixed fluid

We consider the linear heat equation in a domain occupied by a solid material with a network of pipes in which a well-mixed fluid is circulating. The temperature of the fluid in the pipe is uniform and its time variation is determined by the thermal flux on the wall of the pipe, plus a given internal source; continuity of the temperature across the pipe is also assumed. We suppose that we deal with a periodic geometry, with cells of size with inclusions of size r_g; we study in detail in the case r, referring to a previous paper for the case r In the limit »0 we get a homogenized equation. The limit depends strongly on the ratio between the time variation of the temperature in the inclusions and the thermal flux through the interface. The homogenized equation has a new specific heat, which depends on the porosity and the constant of proportionality between the time variation of temperature and the flux on the boundary of the pipe. We also have a new thermal conductivity depending on the microstructure, and volume sources appear. The main tool is the energy method and we generalize the classical results for the more standard boundary conditions for parabolic equations. Finally, we consider the network of pipes forming a random ball structure. We prove convergence for this case. The homogenized equation is of the same form as in the periodic case but auxiliary problems are stochastic.     

Approximation du temps local des surfaces gaussiennes

Summary LetX be a centered stationary Gaussian stochastic process with ad-dimensional parameter (d2),F its spectral measure, (x denotes the Euclidean norm ofx). We consider regularizations of the trajectories ofX by means of convolutions of the formX (t)=( *X)(t) where stands for an approximation of unity (as tends to zero) satisfying certain regularity conditions.The aim of this paper is to recover the local time ofX at a given levelu, as a limit of appropriate normalizations of the geometric measure of theu-level set of the regular approximating processesX . A part of the difficulties comes from the fact that the geometric behavior of the covariance of the Gaussian processX can be a complex one as approaches O.The results are onL ²-convergence and include bounds for the speed of convergence.L ^presults may be obtained in similar ways, but almost sure convergence or simultaneous convergence for the various values ofu do not seem to follow from our methods. In Sect. 3 we have included examples showing a diversity of geometric behaviors, especially in what concerns the dependence on the thickness of the set in which the covariance of the original processX is irregular.Some technical results of analytic nature are included as appendices in Sect. 4.     

Ab initio molecular dynamics simulation of a room temperature ionic liquid

Ab initio molecular dynamics simulations have been performed for the first time on the room-temperature organic ionic liquid dimethyl imidazolium chloride [DMIM][Cl] using density functional theory. The aim is to compare the local liquid structure with both that obtained from two different classical force fields and from neutron scattering experiments. The local structure around the cation shows significant differences compared to both the classical calculations and the neutron results. In particular, and unlike in the gas-phase ion pair, chloride ions tend to be located near a ring C-H proton in a position suggesting hydrogen bonding. The results are used to suggest ways in which the classical potentials may be improved.     

Convergence properties of Hartree–Fock SCF molecular calculations

Hartree-Fock equations are viewed as nonlinear algebraic equations that can be solved iteratively. Provided we assume the existence of a solution, valuable properties of convergence may be assessed. The close connection between convergence of the SCF procedure and stability properties of the solution is shown from a nonapproximate standpoint. The convergence features of level-shifting convergence-forcing techniques are analyzed. The connection between this nonlinear algebraic approach and the related gap equation is displayed and the example of the restricted Hartree-Fock hydrogen molecule is discussed.     

Semiclassical study of collision-induced predissociation: Comparison of the Landau-Zener model with the method of analytic continuation

Semiclassical calculations are carried out by two methods for the problem of collision-induced predissociation of electronically excited I₂. The first method is that of surface-hopping with the Landau-Zener model. The second method is similar to surface-hopping, except that analytic continuation of the adiabatic potential energy surfaces replaces the Landau-Zener model. Results of the calculations by the two methods compare favorably with each other and with experiment. The possible advantages of the second method are discussed.Camille and Henry Dreyfus Teacher-Scholar, Alfred P. Sloan Research Fellow.     

Structural investigation of 3,5‐disubstituted isoxazoles by 1H‐nuclear magnetic resonance

HIV‐1 integrase (IN) is a very promising and validated target for the development of therapeutic agents against AIDS. In an effort to design and synthesize biological isosteric analogs of β‐diketoacid‐containing inhibitors of IN, we prepared a series of substituted isoxazole carboxylic acids. Several of these compounds inhibited catalytic activities of purified IN at micromolar concentration range. With an aim to prepare a large number of analogues based on the isoxazole pharmacophore we focused our study on a series of 3,5‐disubstituted isoxazole isomers. For a rapid structural analysis we discovered a convenient ¹H‐nmr method for distinguishing between isomeric structures based on their H‐4 assignments. This “finger print” approach to isomer identification will be useful in combinatorial chemistry settings where a mixture can be further derivatized.     

New aspects in the reaction of azomethines with cyclic CH-acidic compounds

Summary Treatment of substituted benzylidene anilines1 a – df with cyclic CH-acidic compounds2a–m in ethanol at room temperature yields in additon/elimination reactions the corresponding arylidene derivatives4 and the 2:1 adducts5. The addition products3, which are formed as intermediates, could not be isolated in any case. The donor/acceptor effect of the substituents on the benzylidene moiety influences to a significant extent the reactivity towards the azomethine carbon.

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Neue Aspekte der Reaktion von Azomethinen mit cyclischen CH-aciden Verbindungen

Zusammenfassung Bei der Umsetzung der substituierten Benzylidenaniline1 a – f mit den cyclischen CH-aciden Verbindungen2 a – m in Ethanol bei Raumtemperatur erhält man in Additions/Eliminierungsreaktionen die Arylidenderivate4 und die 2:1-Addukte5. Die als Intermediat gebildeten Additionsprodukte3 konnten in keinem Fall isoliert werden. Die Donor-bzw. Acceptorwirkung der Substituenten am Benzylidenrest beeinflußt maßgebend die Reaktivität am Azomethinkohlenstoff.