Dynamics of Barrierless and Activated Chemical Reactions in a Dispersive Medium within the Fractional Diffusion Equation Approach

Barrierless chemical reactions have often been modeled as a Brownian motion on a one-dimensional harmonic potential energy surface with a position-dependent reaction sink or window located near the minimum of the surface. This simple (but highly successful) description leads to a nonexponential survival probability only at small to intermediate times but exponential decay in the long-time limit. However, in several reactive events involving proteins and glasses, the reactions are found to exhibit a strongly nonexponential (power law) decay kinetics even in the long time. In order to address such reactions, here, we introduce a model of barrierless chemical reaction where the motion along the reaction coordinate sustains dispersive diffusion. A complete analytical solution of the model can be obtained only in the frequency domain, but an asymptotic solution is obtained in the limit of long time. In this case, the asymptotic long-time decay of the survival probability is a power law of the Mittag−Leffler functional form. When the barrier height is increased, the decay of the survival probability still remains nonexponential, in contrast to the ordinary Brownian motion case where the rate is given by the Smoluchowski limit of the well-known Kramers' expression. Interestingly, the reaction under dispersive diffusion is shown to exhibit strong dependence on the initial state of the system, thus predicting a strong dependence on the excitation wavelength for photoisomerization reactions in a dispersive medium. The theory also predicts a fractional viscosity dependence of the rate, which is often observed in the reactions occurring in complex environments.

Approximation of solutions to fractional integral equation

In this paper we shall study a fractional integral equation in an arbitrary Banach space X. We used the analytic semigroups theory of linear operators and the fixed point method to establish the existence and uniqueness of solutions of the given problem. We also prove the existence of global solution. The existence and convergence of the Faedo–Galerkin solution to the given problem is also proved in a separable Hilbert space with some additional assumptions on the operator A. Finally we give an example to illustrate the applications of the abstract results.

Beyond fractional derivatives: local approximation of other convolution integrals

Dynamic systems involving convolution integrals with decaying kernels, of which fractionally damped systems form a special case, are non-local in time and hence infinite dimensional. Straightforward numerical solution of such systems up to time t needs O(t(2)) computations owing to the repeated evaluation of integrals over intervals that grow like t. Finite-dimensional and local approximations are thus desirable. We present here an approximation method which first rewrites the evolution equation as a coupled in finite-dimensional system with no convolution, and then uses Galerkin approximation with finite elements to obtain linear, finite-dimensional, constant coefficient approximations for the convolution. This paper is a broad generalization, based on a new insight, of our prior work with fractional order derivatives (Singh & Chatterjee 2006 Nonlinear Dyn. 45, 183-206). In particular, the decaying kernels we can address are now generalized to the Laplace transforms of known functions; of these, the power law kernel of fractional order differentiation is a special case. The approximation can be refined easily. The local nature of the approximation allows numerical solution up to time t with O(t) computations. Examples with several different kernels show excellent performance. A key feature of our approach is that the dynamic system in which the convolution integral appears is itself approximated using another system, as distinct from numerically approximating just the solution for the given initial values; this allows non-standard uses of the approximation, e. g. in stability analyses.

EXACT INTERNAL CONTROLLABILITY FOR THE WAVE EQUATION IN A DOMAIN WITH OSCILLATING BOUNDARY WITH NEUMANN BOUNDARY CONDITION

In this paper, we study the exact controllability of a second order linear evolution equation in a domain with highly oscillating boundary with homogeneous Neumann boundary condition on the oscillating part of boundary. Our aim is to obtain the exact controllability for the homogenized equation. The limit problem with Neumann condition on the oscillating boundary is different and hence we need to study the exact controllability of this new type of problem. In the process of homogenization, we also study the asymptotic analysis of evolution equation in two setups, namely solution by standard weak formulation and solution by transposition method.

An extended Cahn-Hilliard model for interfaces with cubic anisotropy

For studying systems with a cubic anisotropy in interfacial energy sigma, we extend the Cahn-Hilliard model by including in it a fourth-rank term, namely, gamma (ijlm) [partial derivative (2) c/(partial derivativex(i) partial derivativex(j))] [partial derivative (2) c/(partial derivativex(l) partial derivativex(m))]. This term leads to an additional linear term in the evolution equation for the composition parameter field. It also leads to an orientation-dependent effective fourth-rank coefficient gamma ([hkl]) in the governing equation for the one-dimensional composition profile across a planar interface. The main effect of a non-negative gamma ([hkl]) is to increase both sigma and interfacial width w, each of which, upon suitable scaling, is related to gamma ([hkl]) through a universal scaling function. In this model, sigma is a differentiable function of interface orientation (n) over cap, and does not exhibit cusps; therefore, the equilibrium particle shapes (Wulff shapes) do not contain planar facets. However, the anisotropy in the interfacial energy can be large enough to give rise to corners in the Wulff shapes in two dimensions. In particles of finite sizes, the corners become rounded, and their shapes tend towards the Wulff shape with increasing particle size.

Arbitrary Lagrangian-Eulerian finite-element method for computation of two-phase flows with soluble surfactants

A finite-element scheme based on a coupled arbitrary Lagrangian-Eulerian and Lagrangian approach is developed for the computation of interface flows with soluble surfactants. The numerical scheme is designed to solve the time-dependent Navier-Stokes equations and an evolution equation for the surfactant concentration in the bulk phase, and simultaneously, an evolution equation for the surfactant concentration on the interface. Second-order isoparametric finite elements on moving meshes and second-order isoparametric surface finite elements are used to solve these equations. The interface-resolved moving meshes allow the accurate incorporation of surface forces, Marangoni forces and jumps in the material parameters. The lower-dimensional finite-element meshes for solving the surface evolution equation are part of the interface-resolved moving meshes. The numerical scheme is validated for problems with known analytical solutions. A number of computations to study the influence of the surfactants in 3D-axisymmetric rising bubbles have been performed. The proposed scheme shows excellent conservation of fluid mass and of the total mass of the surfactant. (C) 2012 Elsevier Inc. All rights reserved.

On the curvature ODE associated to the Ricci flow

In the vector space of algebraic curvature operators we study the reaction ODE which is associated to the evolution equation of the Riemann curvature operator along the Ricci flow. More precisely, we give a partial classification of the zeros of this ODE up to suitable normalization and analyze the stability of a special class of zeros of the same. In particular, we show that the ODE is unstable near the curvature operators of the Riemannian product spaces where is an Einstein (locally) symmetric space of compact type and not a spherical space form when .

Single Spin Asymmetry in Charmonium Production

We present estimates of single spin asymmetry (SSA) in the electroproduction of taking into account the transverse momentum dependent (TMD) evolution of the gluon Sivers function and using Color Evaporation Model of charmonium production. We estimate SSA for JLab, HERMES, COMPASS and eRHIC energies using recent parameters for the quark Sivers functions which are fitted using an evolution kernel in which the perturbative part is resummed up to next-to-leading logarithms accuracy. We find that these SSAs are much smaller as compared to our first estimates obtained using DGLAP evolution but are comparable to our estimates obtained using TMD evolution where we had used approximate analytical solution of the TMD evolution equation for the purpose.

An evolutionary formalism for weak quantum measurements

Unitary evolution and projective measurement are fundamental axioms of quantum mechanics. Even though projective measurement yields one of the eigenstates of the measured operator as the outcome, there is no theory that predicts which eigenstate will be observed in which experimental run. There exists only an ensemble description, which predicts probabilities of various outcomes over many experimental runs. We propose a dynamical evolution equation for the projective collapse of the quantum state in individual experimental runs, which is consistent with the well-established framework of quantum mechanics. In case of gradual weak measurements, its predictions for ensemble evolution are different from those of the Born rule. It is an open question whether or not suitably designed experiments can observe this alternate evolution.

3-D kinematical conservation laws (KCL): Evolution of a surface in R-3 - in particular propagation of a nonlinear wavefront

3-D KCL are equations of evolution of a propagating surface (or a wavefront) Omega(t), in 3-space dimensions and were first derived by Giles, Prasad and Ravindran in 1995 assuming the motion of the surface to be isotropic. Here we discuss various properties of these 3-D KCL.These are the most general equations in conservation form, governing the evolution of Omega(t) with singularities which we call kinks and which are curves across which the normal n to Omega(t) and amplitude won Omega(t) are discontinuous. From KCL we derive a system of six differential equations and show that the KCL system is equivalent to the ray equations of 2, The six independent equations and an energy transport equation (for small amplitude waves in a polytropic gas) involving an amplitude w (which is related to the normal velocity m of Omega(t)) form a completely determined system of seven equations. We have determined eigenvalues of the system by a very novel method and find that the system has two distinct nonzero eigenvalues and five zero eigenvalues and the dimension of the eigenspace associated with the multiple eigenvalue 0 is only 4. For an appropriately defined m, the two nonzero eigenvalues are real when m > 1 and pure imaginary when m < 1. Finally we give some examples of evolution of weakly nonlinear wavefronts.

An Online Implementable Differential Evolution Tuned Optimal Guidance Law

This paper proposes a novel application of differential evolution to solve a difficult dynamic optimisation or optimal control problem. The miss distance in a missile-target engagement is minimised using differential evolution. The difficulty of solving it by existing conventional techniques in optimal control theory is caused by the nonlinearity of the dynamic constraint equation, inequality constraint on the control input and inequality constraint on another parameter that enters problem indirectly. The optimal control problem of finding the minimum miss distance has an analytical solution subject to several simplifying assumptions. In the approach proposed in this paper, the initial population is generated around the seed value given by this analytical solution. Thereafter, the algorithm progresses to an acceptable final solution within a few generations, satisfying the constraints at every iteration. Since this solution or the control input has to be obtained in real time to be of any use in practice, the feasibility of online implementation is also illustrated.

Combined Atomic Force Microscopy and Modeling Study of The Evolution of Octadecylamine Films on a Mica Surface

The time evolution of the film thickness and domain formation of octadecylamine molecules adsorbed oil a mica surface is investigated Using atomic force microscopy. The adsorbed Film thickness is determined by measuring the height profile across the mica-amine interface of a mica surface partially immersed in a 15 mM solution of octadecylamine in chloroform. Using this novel procedure, adsorption of amine on mica is found to occur in three distinct stages, with morphologically distinct domain Formation and growth occurring during each stage. In the first stage, where adsorption is primarily in the thin-film regime, all average Film thickness of 0.2 (+/- 0.3) nm is formed for exposure times below 30 s and 0.8 (+/- 0.2) nm for 60 s of immersion time. During this stage, large sample spanning domains are observed. The second stage, which occurs between 60-300 s, is associated with it regime of rapid film growth, and the film thickness increases from about 0.8 to 25 nm during this stage. Once the thick-film regime is established, further exposure to the amine solution results in all increase in the domain area, and it regime of lateral domain growth is observed. In this stage, the domain area coverage grows from 38 to 75%, and the FTIR spectra reveal an increased level of crystallinity in the film. Using it diffusion-controlled model and it two-step Langmuir isotherm, the time evolution of the film growth is quantitatively captured. The model predicts the time at which the thin to thick film transition occurs as well its the time required for complete film growth at longer times. The Ward-Tordai equation is also solved to determine the model parameters in the monolayer (thin-film) regime, which occurs during the initial stages of film growth.

Polymer melt dynamics: Microscopic roots of fractional viscoelasticity

The rheological properties of polymer melts and other complex macromolecular fluids are often successfully modeled by phenomenological constitutive equations containing fractional differential operators. We suggest a molecular basis for such fractional equations in terms of the generalized Langevin equation (GLE) that underlies the renormalized Rouse model developed by Schweizer [J. Chem. Phys. 91, 5802 (1989)]. The GLE describes the dynamics of the segments of a tagged chain under the action of random forces originating in the fast fluctuations of the surrounding polymer matrix. By representing these random forces as fractional Gaussian noise, and transforming the GLE into an equivalent diffusion equation for the density of the tagged chain segments, we obtain an analytical expression for the dynamic shear relaxation modulus G(t), which we then show decays as a power law in time. This power-law relaxation is the root of fractional viscoelastic behavior.

Existence and approximations of solutions to some fractional order functional integral equations

In this paper we shall study a fractional order functional integral equation. In the first part of the paper, we proved the existence and uniqueness of mile and global solutions in a Banach space. In the second part of the paper, we used the analytic semigroups theory oflinear operators and the fixed point method to establish the existence, uniqueness and convergence of approximate solutions of the given problem in a separable Hilbert space. We also proved the existence and convergence of Faedo-Galerkin approximate solution to the given problem. Finally, we give an example.

Unified Galerkin- and DAE-Based Approximation of Fractional Order Systems

We consider numerical solutions of nonlinear multiterm fractional integrodifferential equations, where the order of the highest derivative is fractional and positive but is otherwise arbitrary. Here, we extend and unify our previous work, where a Galerkin method was developed for efficiently approximating fractional order operators and where elements of the present differential algebraic equation (DAE) formulation were introduced. The DAE system developed here for arbitrary orders of the fractional derivative includes an added block of equations for each fractional order operator, as well as forcing terms arising from nonzero initial conditions. We motivate and explain the structure of the DAE in detail. We explain how nonzero initial conditions should be incorporated within the approximation. We point out that our approach approximates the system and not a specific solution. Consequently, some questions not easily accessible to solvers of initial value problems, such as stability analyses, can be tackled using our approach. Numerical examples show excellent accuracy. DOI: 10.1115/1.4002516]