Goal-oriented sensitivity analysis for lattice kinetic Monte Carlo simulations

• Published in: The Journal of chemical physics Vol. 140; no. 12; p. 124108
• Main Authors: Arampatzis, Georgios, Katsoulakis, Markos A.
• Format: Journal Article
• Language: English
• Published: United States American Institute of Physics 28.03.2014
• Subjects: ADSORPTION; Algorithms; Computer simulation; COMPUTERIZED SIMULATION; Confidence intervals; COUPLINGS; DESORPTION; Diagnostic software; Diagnostic systems; Dimensional analysis; EVALUATION; Finite difference method; HAMILTONIANS; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Kinetics; Markov chains; MINIMIZATION; Molecular Dynamics Simulation; MONTE CARLO METHOD; Monte Carlo simulation; Random numbers; SENSITIVITY ANALYSIS; Source code; Stochastic Processes; Stochastic systems; Surface roughness; Variance
• ISSN: 0021-9606; 1089-7690; 1089-7690
• DOI: 10.1063/1.4868649

In this paper we propose a new class of coupling methods for the sensitivity analysis of high dimensional stochastic systems and in particular for lattice Kinetic Monte Carlo (KMC). Sensitivity analysis for stochastic systems is typically based on approximating continuous derivatives with respect to model parameters by the mean value of samples from a finite difference scheme. Instead of using independent samples the proposed algorithm reduces the variance of the estimator by developing a strongly correlated-“coupled”- stochastic process for both the perturbed and unperturbed stochastic processes, defined in a common state space. The novelty of our construction is that the new coupled process depends on the targeted observables, e.g., coverage, Hamiltonian, spatial correlations, surface roughness, etc., hence we refer to the proposed method as goal-oriented sensitivity analysis. In particular, the rates of the coupled Continuous Time Markov Chain are obtained as solutions to a goal-oriented optimization problem, depending on the observable of interest, by considering the minimization functional of the corresponding variance. We show that this functional can be used as a diagnostic tool for the design and evaluation of different classes of couplings. Furthermore, the resulting KMC sensitivity algorithm has an easy implementation that is based on the Bortz–Kalos–Lebowitz algorithm's philosophy, where events are divided in classes depending on level sets of the observable of interest. Finally, we demonstrate in several examples including adsorption, desorption, and diffusion Kinetic Monte Carlo that for the same confidence interval and observable, the proposed goal-oriented algorithm can be two orders of magnitude faster than existing coupling algorithms for spatial KMC such as the Common Random Number approach. We also provide a complete implementation of the proposed sensitivity analysis algorithms, including various spatial KMC examples, in a supplementary MATLAB source code.