Manifestation of conical intersections in resonance Raman intensities

This paper deals with the manifestations of conical intersections (CIs), unequivocal spectroscopic signatures of which are still elusive, in the resonance Raman intensities. In particular, the results of our calculations on the `two state-two vibrational mode' and the `two state-three vibrational mode' models are presented. The models comprise two excited states of different spatial symmetry, one bright and one dark, which are coupled by a nontotally symmetric mode while the energy gap between them is tuned by one/two totally symmetric modes. Time dependent theory for vibronically coupled states is employed for the calculation and analysis of Raman excitation profiles (REPs). The manifestation of intersections in REPs is studied by extensive modelm calculations and the results of two specific models are presented. Themfeasibility of using REPs to probe the role of CIs in polyatomic systems is ascertained by multimode calculations on two polyatomic systems viz., pyrazine and trans-azobenzene. The study also notes the importance of the pump excitation wavelength dependence in a femtosecond time-resolved experiment probing the intersection-induced nonadiabatic dynamics. Copyright (C) 2009 John Wiley & Sons, Ltd.

Reinforcement learning with average cost for adaptive control of traffic lights at intersections

We propose for the first time two reinforcement learning algorithms with function approximation for average cost adaptive control of traffic lights. One of these algorithms is a version of Q-learning with function approximation while the other is a policy gradient actor-critic algorithm that incorporates multi-timescale stochastic approximation. We show performance comparisons on various network settings of these algorithms with a range of fixed timing algorithms, as well as a Q-learning algorithm with full state representation that we also implement. We observe that whereas (as expected) on a two-junction corridor, the full state representation algorithm shows the best results, this algorithm is not implementable on larger road networks. The algorithm PG-AC-TLC that we propose is seen to show the best overall performance.

Effects of two-wheelers on saturation flow at signalized intersections in developing countries

Two-wheelers (TW) constitute a major proportion of urban traffic in developing countries and therefore their effect on the saturation flow at signalized intersections could be substantial. This paper attempts to study and analyze the effect of two-wheelers on the saturation flow of signalized intersections by collecting data at a few signalized intersections in Bangalore, India. A strong correlation is observed between the measured saturation flow and the proportion of two-wheeler traffic, which suggest that two-wheelers have significant impact and should be considered in the capacity analysis of signalized intersections. In this paper, the effect of two-wheelers on saturation flow rate is incorporated in a previous model by calibrating and introducing a new adjustment factor for two-wheelers. Results show that saturation flow measured using the modified HCM equation is closer to observed saturation flow values.

Geometry of the de-Sitter universe

By making use of the fact that the de-Sitter metric corresponds to a hyperquadric in a five-dimensional flat space, it is shown that the three Robertson-Walker metrics for empty spacetime and positive cosmological constant, corresponding to 3-space of positive, negative and zero curvative, are geometrically equivalent. The 3-spaces correspond to intersections of the hyperquadric by hyperplanes, and the time-like geodesics perpendicular to them correspond to intersections by planes, in all three cases.

Nonlinear dynamics of a rigid block on a rigid base

The planar rocking of a prismatic rectangular rigid block about either of its corners is considered. The problem of homoclinic intersections of the stable and unstable manifolds of the perturbed separatrix is addressed to and the corresponding Melnikov functions are derived. Inclusion of the vertical forcing in the Hamiltonian permits the construction of a three-dimensional separatrix. The corresponding modified Melnikov function of Wiggins for homoclinic intersections is derived. Further, the 1-period symmetric orbits are predicted analytically using the method of averaging and compared with the simulation results. The stability boundary for such orbits is also established.

Relation between integral and partial properties of ternary solutions along different composition trajectories

The relations between partial and integral properties of ternary solutions along composition trajectories suggested by Kohler, Colinet and Jacob, and along an arbitrary path are derived. The chemical potentials of the components are related to the slope of integral free energy by expressions involving the binary compositions generated by the intersections of the composition trajectory with the sides of the ternary triangle. Only along the Kohler composition trajectory it is possible to derive the integral free energy from the variation of the chemical potential of a single component with composition or vice versa. Along all other paths the differential of the integral free energy is related to two chemical potentials. The Gibbs-Duhem integration proposed by Darken for the ternary system uses the Kohler isogram. The relative merits of different limits for integration are discussed.

Bases and Ideal Generators for Projective Monomial Curves

In this article we study bases for projective monomial curves and the relationship between the basis and the set of generators for the defining ideal of the curve. We understand this relationship best for curves in P-3 and for curves defined by an arithmetic progression. We are able to prove that the latter are set theoretic complete intersections.

Theoretical analysis of photoinduced H-atom elimination in thiophenol

The photoinduced hydrogen elimination reaction in thiophenol via the conical intersections of the dissociative (1)pi sigma* excited state with the bound (1)pi pi* excited state and the electronic ground state has been investigated with ab initio electronic-structure calculations and time-dependent quantum wave-packet calculations. A screening of the coupling constants of the symmetry-allowed coupling modes at the (1)pi pi*-(1)pi sigma* and (1)pi sigma*-S-0 conical intersection shows that the SH torsional mode is by far the most important coupling mode at both conical intersections. A model including three intersecting potential-energy surfaces (S-0, (1)pi pi*, (1)pi sigma*) and two nuclear degrees of freedom (SH stretch and SH torsion) has been constructed on the basis of ab initio complete-active-space self-consistent field and multireference second-order perturbation theory calculations. The nonadiabatic quantum wave-packet dynamics initiated by optical excitation of the (1)pi pi* and (1)pi sigma* states has been explored for this three-state two-coordinate model. The photodissociation dynamics is characterized in terms of snapshots of time-dependent wave packets, time-dependent electronic population probabilities, and the branching ratio of the (2)sigma/(2)pi electronic states of the thiophenoxyl radical. The dependence of the timescale of the photodissociation process and the branching ratio on the initial excitation of the SH stretching and SH torsional vibrations has been analyzed. It is shown that the node structure, which is imposed on the nuclear wave packets by the initial vibrational preparation as well as by the transitions through the conical intersections, has a profound effect on the photodissociation dynamics. The effect of additional weak coupling modes of CC twist (nu(16a)) and ring-distortion (nu(16b)) character has been investigated with three-dimensional and four-dimensional time-dependent wave-packet calculations, and has been found to be minor. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4709608]

On piercing (pseudo)lines and boxes

We say a family of geometric objects C has (l;k)-property if every subfamily C0C of cardinality at most lisk- piercable. In this paper we investigate the existence of g(k;d)such that if any family of objects C in Rd has the (g(k;d);k)-property, then C is k-piercable. Danzer and Gr̈ unbaum showed that g(k;d)is infinite for fami-lies of boxes and translates of centrally symmetric convex hexagons. In this paper we show that any family of pseudo-lines(lines) with (k2+k+ 1;k)-property is k-piercable and extend this result to certain families of objects with discrete intersections. This is the first positive result for arbitrary k for a general family of objects. We also pose a relaxed ver-sion of the above question and show that any family of boxes in Rd with (k2d;k)-property is 2dk- piercable.

Experimental study of fracture behavior of magnesium single crystals

In this work, the fracture behavior of magnesium single crystals is studied by conducting experiments with notched three point bend specimens of three crystallographic orientations. In the first and second orientations, the c-axis is along the normal to the flat surface of the notch, while in the third it is aligned with the notch front. For all the orientations, in situ electron back scattered diffraction observations made around the notch root show profuse tensile twinning of {10 (1) over bar2} type. Further, in the first two orientations basal and prismatic slip traces are identified from optical metallography. The width of the most prominent twin saturates at around 120-150 mu m, while twins continue to nucleate farther away to accommodate plastic deformation. In all the orientations, crack initiation occurs before the attainment of peak load and the crack grows stably along twin-matrix interface before deflecting at twin-twin intersections. Results show that profuse tensile twinning is an important energy dissipating mechanism that enhances the fracture toughness. (C) 2013 Elsevier B.V. All rights reserved.

Nodal domains of the equilateral triangle billiard

We characterize the eigenfunctions of an equilateral triangle billiard in terms of its nodal domains. The number of nodal domains has a quadratic form in terms of the quantum numbers, with a non-trivial number-theoretic factor. The patterns of the eigenfunctions follow a group-theoretic connection in a way that makes them predictable as one goes from one state to another. Extensive numerical investigations bring out the distribution functions of the mode number and signed areas. The statistics of the boundary intersections is also treated analytically. Finally, the distribution functions of the nodal loop count and the nodal counting function are shown to contain information about the classical periodic orbits using the semiclassical trace formula. We believe that the results belong generically to non-separable systems, thus extending the previous works which are concentrated on separable and chaotic systems.

Freeform Skeletal Shape Optimization of Compliant Mechanisms

Compliant mechanisms are elastic continua used to transmit or transform force and motion mechanically. The topology optimization methods developed for compliant mechanisms also give the shape for a chosen parameterization of the design domain with a fixed mesh. However, in these methods, the shapes of the flexible segments in the resulting optimal solutions are restricted either by the type or the resolution of the design parameterization. This limitation is overcome in this paper by focusing on optimizing the skeletal shape of the compliant segments in a given topology. It is accomplished by identifying such segments in the topology and representing them using Bezier curves. The vertices of the Bezier control polygon are used to parameterize the shape-design space. Uniform parameter steps of the Bezier curves naturally enable adaptive finite element discretization of the segments as their shapes change. Practical constraints such as avoiding intersections with other segments, self-intersections, and restrictions on the available space and material, are incorporated into the formulation. A multi-criteria function from our prior work is used as the objective. Analytical sensitivity analysis for the objective and constraints is presented and is used in the numerical optimization. Examples are included to illustrate the shape optimization method.

Finite element simulations of notch tip fields in magnesium single crystals

Recent experiments using three point bend specimens of Mg single crystals have revealed that tensile twins of {10 (1) over bar2}-type form profusely near a notch tip and enhance the fracture toughness through large plastic dissipation. In this work, 3D finite element simulations of these experiments are carried out using a crystal plasticity framework which includes slip and twinning to gain insights on the mechanics of fracture. The predicted load-displacement curves, slip and tensile twinning activities from finite element analysis corroborate well with the experimental observations. The numerical results are used to explore the 3D nature of the crack tip stress, plastic slip and twin volume fraction distributions near the notch root. The occurrence of tensile twinning is rationalized from the variation of normal stress ahead of the notch tip. Further, deflection of the crack path at twin-twin intersections observed in the experiments is examined from an energy standpoint by modeling discrete twins close to the notch root.

A Smooth Discretization Bridging Finite Element and Mesh-free Methods Using Polynomial Reproducing Simplex Splines

This work sets forth a `hybrid' discretization scheme utilizing bivariate simplex splines as kernels in a polynomial reproducing scheme constructed over a conventional Finite Element Method (FEM)-like domain discretization based on Delaunay triangulation. Careful construction of the simplex spline knotset ensures the success of the polynomial reproduction procedure at all points in the domain of interest, a significant advancement over its precursor, the DMS-FEM. The shape functions in the proposed method inherit the global continuity (Cp-1) and local supports of the simplex splines of degree p. In the proposed scheme, the triangles comprising the domain discretization also serve as background cells for numerical integration which here are near-aligned to the supports of the shape functions (and their intersections), thus considerably ameliorating an oft-cited source of inaccuracy in the numerical integration of mesh-free (MF) schemes. Numerical experiments show the proposed method requires lower order quadrature rules for accurate evaluation of integrals in the Galerkin weak form. Numerical demonstrations of optimal convergence rates for a few test cases are given and the method is also implemented to compute crack-tip fields in a gradient-enhanced elasticity model.

A stabilization approach for mesh-free simulations of systems developing shocks or extreme strain localizations

A new stabilization scheme, based on a stochastic representation of the discretized field variables, is proposed with a view to reduce or even eliminate unphysical oscillations in the mesh-free numerical simulations of systems developing shocks or exhibiting localized bands of extreme deformation in the response. The origin of the stabilization scheme may be traced to nonlinear stochastic filtering and, consistent with a class of such filters, gain-based additive correction terms are applied to the simulated solution of the system, herein achieved through the element-free Galerkin method, in order to impose a set of constraints that help arresting the spurious oscillations. The method is numerically illustrated through its Applications to inviscid Burgers' equations, wherein shocks may develop as a result of intersections of the characteristics, and to a gradient plasticity model whose response is often characterized by a developing shear band as the external load is gradually increased. The potential of the method in stabilized yet accurate numerical simulations of such systems involving extreme gradient variations in the response is thus brought forth. (C) 2014 Elsevier Ltd. All rights reserved.