This review provides a pedagogic and self-contained introduction to master equations and to their representation by path integrals. Since the 1930s, master equations have served as a fundamental tool to understand the role of fluctuations in complex biological, chemical, and physical systems. Despite their simple appearance, analyses of master equations most often rely on low-noise approximations such as the Kramers-Moyal or the system size expansion, or require ad-hoc closure schemes for the derivation of low-order moment equations. We focus on numerical and analytical methods going beyond the low-noise limit and provide a unified framework for the study of master equations. After deriving the forward and backward master equations from the Chapman-Kolmogorov equation, we show how the two master equations can be cast into either of four linear partial differential equations (PDEs). Three of these PDEs are discussed in detail. The first PDE governs the time evolution of a generalized probability generating function whose basis depends on the stochastic process under consideration. Spectral methods, WKB approximations, and a variational approach have been proposed for the analysis of the PDE. The second PDE is novel and is obeyed by a distribution that is marginalized over an initial state. It proves useful for the computation of mean extinction times. The third PDE describes the time evolution of a 'generating functional', which generalizes the so-called Poisson representation. Subsequently, the solutions of the PDEs are expressed in terms of two path integrals: a 'forward' and a 'backward' path integral. Combined with inverse transformations, one obtains two distinct path integral representations of the conditional probability distribution solving the master equations. We exemplify both path integrals in analysing elementary chemical reactions. Moreover, we show how a well-known path integral representation of averaged observables can be recovered from them. Upon expanding the forward and the backward path integrals around stationary paths, we then discuss and extend a recent method for the computation of rare event probabilities. Besides, we also derive path integral representations for processes with continuous state spaces whose forward and backward master equations admit Kramers-Moyal expansions. A truncation of the backward expansion at the level of a diffusion approximation recovers a classic path integral representation of the (backward) Fokker-Planck equation. One can rewrite this path integral in terms of an Onsager-Machlup function and, for purely diffusive Brownian motion, it simplifies to the path integral of Wiener. To make this review accessible to a broad community, we have used the language of probability theory rather than quantum (field) theory and do not assume any knowledge of the latter. The probabilistic structures underpinning various technical concepts, such as coherent states, the Doi-shift, and normal-ordered observables, are thereby made explicit.
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http://dx.doi.org/10.1088/1361-6633/aa5ae2 | DOI Listing |
Phys Chem Chem Phys
January 2025
Wolfson Department of Chemical Engineering, Technion - Israel Institute of Technology, Haifa 3200003, Israel.
The pressure-dependent reactions on the NH potential energy surface (PES) have been investigated using CCSD(T)-F12/aug-cc-pVTZ-F12//B2PLYP-D3/aug-cc-pVTZ. This study expands the NH PES beyond the previous literature by incorporating a newly identified isomer, NHN, along with additional bimolecular reaction channels associated with this isomer, namely NNH + H and HNN(S) + H. Rate coefficients for all relevant pressure-dependent reactions, including well-skipping pathways, are predicted using a combination of transition state theory and master equation simulations.
View Article and Find Full Text PDFWe study Hopfield networks with non-reciprocal coupling inducing switches between memory patterns. Dynamical phase transitions occur between phases of no memory retrieval, retrieval of multiple point-attractors, and limit-cycle attractors. The limit cycle phase is bounded by two critical regions: a Hopf bifurcation line and a fold bifurcation line, each with unique dynamical critical exponents and sensitivity to perturbations.
View Article and Find Full Text PDFJ Robot Surg
January 2025
Department of Urology, The First Affiliated Hospital of Guangzhou Medical University, Guangzhou, 510230, Guangdong, China.
This study applied cumulative sum (CUSUM) analysis to evaluate trends in operative time and blood loss, It aims to identify key milestones in mastering extraperitoneal single-site robotic-assisted radical prostatectomy (ss-RARP). A cohort of 100 patients who underwent ss-RARP, performed by a single surgeon at the First Affiliated Hospital of Guangzhou Medical University between March 2021 and June 2023, was retrospectively analyzed. To evaluate the learning curve, the CUSUM (Cumulative Sum Control Chart) technique was applied, revealing the progression and variability over time.
View Article and Find Full Text PDFJ Chem Phys
January 2025
School of Chemistry and Chemical Engineering and Chongqing Key Laboratory of Chemical Theory and Mechanism, Chongqing University, Chongqing 401331, China.
The reaction CH3NC ⇌ CH3CN, a model reaction for the study of unimolecular isomerization, is important in astronomy and atmospheric chemistry and has long been studied by numerous experiments and theories. In this work, we report the first full-dimensional accurate potential energy surface (PES) of this reaction by the permutation invariant polynomial-neural network method based on 30 974 points, whose energies are calculated at the CCSD(T)-F12a/AVTZ level. Then, ring polymer molecular dynamics is used to derive the free energy barrier of the reaction at the experimental temperature range of 472.
View Article and Find Full Text PDFInsects
December 2024
Department of Sustainable Crop Production (DiProVeS), Università Cattolica del Sacro Cuore di Piacenza, 29122 Piacenza, Italy.
Background: Mating disruption (MD) is a worthwhile technique for the control of and in central Europe and Mediterranean areas. MD efficacy is affected by the pheromone release (PR), which in turn is influenced by environmental conditions.
Methods: The effect of weather conditions on PR was evaluated under four different fields in northern Italy.
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