Spin-orbit mixing and nephelauxetic effects in the electronic spectra of nickel(II)-encapsulating complexes involving nitrogen and sulfur donors

A study of spin-orbit mixing and nephelauxetic effects in the electronic spectra of nickel(II)-encapsulating complexes involving mixed nitrogen and sulfur donors is reported. As the number of sulfur donors is systematically varied through the series [Ni(N6-xSx)](2+) (x = 0-6), the spin-forbidden (3)A(2)g --> E-1(g) and (3)A(2g) --> (1)A(1g) transitions undergo a considerable reduction in energy whereas the spin-allowed transitions are relatively unchanged. The [Ni(diAMN(6)sar)](2+) and [Ni(AMN(5)Ssar)](2+) complexes exhibit an unusual band shape for the (3)A(2g) --> T-3(2g) transition which is shown to arise from spin-orbit mixing of the E spin-orbit levels associated with the E-1(g) and T-3(2g) states. A significant differential nephelauxetic effect also arises from the covalency differences between the t(2g) and e(g) orbitals with the result that no single set of Racah B and C interelectron repulsion parameters adequately fit the observed spectra. Using a differential covalency ligand-field model, the spectral transitions are successfully reproduced with three independent variables corresponding to 10Dq and the covalency parameters f(t) and f(e), associated with the t(2g) and e(g) orbitals, respectively. The small decrease in f(t) from unity is largely attributed to central-field covalency effects whereas the dramatic reduction in f(e) with increasing number of sulfur donors is a direct consequence of the increased metal-ligand covalency associated with the sulfur donors. Covalency differences between the t(2g) and e(g) orbitals also result in larger 10Dq values than those obtained simply from the energy of the (3)A(2g) --> T-3(2g) spin-allowed transition.

Structure optimization combining soft-core interaction functions, the diffusion equation method, and molecular dynamics

Smoothing the potential energy surface for structure optimization is a general and commonly applied strategy. We propose a combination of soft-core potential energy functions and a variation of the diffusion equation method to smooth potential energy surfaces, which is applicable to complex systems such as protein structures; The performance of the method was demonstrated by comparison with simulated annealing using the refinement of the undecapeptide Cyclosporin A as a test case. Simulations were repeated many times using different initial conditions and structures since the methods are heuristic and results are only meaningful in a statistical sense.

Infrared seeded parametric four-wave mixing for sensitive detection of molecules

We have developed a sensitive resonant four-wave mixing technique based on two-photon parametric four-wave mixing with the addition of a phase matched ''seeder'' field. Generation of the seeder field via the same four-wave mixing process in a high pressure cell enables automatic phase matching to be achieved in a low pressure sample cell. This arrangement facilitates sensitive detection of complex molecular spectra by simply tuning the pump laser. We demonstrate the technique with the detection of nitric oxide down to concentrations more than 4 orders of magnitude below the capability of parametric four-wave mixing alone, with an estimated detection threshold of 10(12) molecules/cm(3).

Introduction to Discounted Cash Flow Analysis and Financial Functions in Excel

The financial and economic analysis of investment projects is typically carried out using the technique of discounted cash flow (DCF) analysis. This module introduces concepts of discounting and DCF analysis for the derivation of project performance criteria such as net present value (NPV), internal rate of return (IRR) and benefit to cost (B/C) ratios. These concepts and criteria are introduced with respect to a simple example, for which calculations using MicroSoft Excel are demonstrated.

A simple solution of the laminar dam break wave

The sudden release of a mass of fluid in a channel generates a highly unsteady flow motion, called dam break wave. While industrial fluids exhibit sometimes non-Newtonian behaviours, the viscous fluid flow assumption remains a useful approximation for simplified analyses. In this study, new solutions of laminar dam break wave are proposed for a semi-infinite reservoir based upon the method of characteristics. The solutions yield simple explicit expressions of the wave front location, wave front celerity and instantaneous free-surface profiles that compare favourably with experimental observations. Both horizontal and sloping channel configurations are treated. The simplicity of the equations may allow future extension to more complicated fluid flows.

Integrable anisotropic spin-ladder model

We present an integrable spin-ladder model, which possesses a free parameter besides the rung coupling J. Wang's system based on the SU(4) symmetry can be obtained as a special case. The model is exactly solvable by means of the Bethe ansatz method. We determine the dependence on the anisotropy parameter of the phase transition between gapped and gapless spin excitations and present the phase diagram. Finally, we show that the model is a special case of a more general Hamiltonian with three free parameters.

Izergin-Korepin model with a boundary

The Izergin-Korepin model on a semi-infinite lattice is diagonalized by using the level-one vertex operators of the twisted quantum affine algebra U-q[((2))(2)]. We give the bosonization of the vacuum state with zero particle content. Excitation states are given by the action of the vertex operators on the vacuum state. We derive the boundary S-matrix. We give an integral expression of the correlation functions of the boundary model, and derive the difference equations which they satisfy. (C) 2001 Elsevier Science B.V. All rights reserved.

Analytical solution and numerical model for the interface in a stratified long wave system

For a two layered long wave propagation, linearized governing equations, which were derived earlier from the Euler equations of mass and momentum assuming negligible friction and interfacial mixing are solved analytically using Fourier transform. For the solution, variations of upper layer water level is assumed to be sinosoidal having known amplitude and variations of interface level is solved. As the governing equations are too complex to solve it analytically, density of upper layer fluid is assumed as very close to the density of lower layer fluid to simplify the lower layer equation. A numerical model is developed using the staggered leap-forg scheme for computation of water level and discharge in one dimensional propagation having known amplitude for the variations of upper layer water level and interface level to be solved. For the numerical model, water levels (upper layer and interface) at both the boundaries are assumed to be known from analytical solution. Results of numerical model are verified by comparing with the analytical solutions for different time period. Good agreements between analytical solution and numerical model are found for the stated boundary condition. The reliability of the developed numerical model is discussed, using it for different a (ratio of density of fluid in the upper layer to that in the lower layer) and p (ratio of water depth in the lower layer to that in the upper layer) values. It is found that as ‘CX’ increases amplification of interface also increases for same upper layer amplitude. Again for a constant lower layer depth, as ‘p’ increases amplification of interface. also increases for same upper layer amplitude.

Integrable open boundary conditions for the Bariev model of three coupled X Y spin chains

The integrable open-boundary conditions for the Bariev model of three coupled one-dimensional XY spin chains are studied in the framework of the boundary quantum inverse scattering method. Three kinds of diagonal boundary K-matrices leading to nine classes of possible choices of boundary fields are found and the corresponding integrable boundary terms are presented explicitly. The boundary Hamiltonian is solved by using the coordinate Bethe ansatz technique and the Bethe ansatz equations are derived. (C) 2001 Elsevier Science B.V. All rights reserved.

Analysis of Piezoelectric sensor to detect flexural waves

The electromechanical transfer characteristics of adhesively bonded piezoelectric sensors are investigated. By the use of dynamic piezoelectricity theory, Mindlin plate theory for flexural wave propagation, and a multiple integral transform method, the frequency-response functions of piezoelectric sensors with and without backing materials are developed and the pressure-voltage transduction functions of the sensors calculated. The corresponding simulation results show that the sensitivity of the sensors is not only dependent on the sensors' inherent features, such as piezoelectric properties and geometry, but also on local characteristics of the tested structures and the admittance and impedance of the attached electrical circuit. It is also demonstrated that the simplified rigid mass sensor model can be used to analyze successfully the sensitivity of the sensor at low frequencies, but that the dynamic piezoelectric continuum model has to be used for higher frequencies, especially around the resonance frequency of the coupled sensor-structure vibration system.