Forward-Flux Sampling with Jumpy Order Parameters

Abstract

Forward-flux sampling (FFS) is a path sampling technique that has gained increased popularity in recent years, and has been used to compute rates of rare event phenomena such as crystallization, condensation, hydrophobic evaporation, DNA hybridization and protein folding. The popularity of FFS is not only due to its ease of implementation, but also because it is not very sensitive to the particular choice of an order parameter. The order parameter utilized in conventional FFS, however, still needs to satisfy a stringent smoothness criterion in order to assure sequential crossing of FFS milestones. This condition is usually violated for order parameters utilized for describing aggregation phenomena such as crystallization. Here, we present a generalized FFS algorithm for which this smoothness criterion is no longer necessary, and apply it to compute homogeneous crystal nucleation rates in several systems. Our numerical tests reveal that conventional FFS can sometimes underestimate the nucleation rate by several orders of magnitude.

28 pages, 8 figures, 2 tables, 2 algorithms

References in corpus (11)

• Accurate determination of crystal structures based on averaged local bond order parameters
• Forward Flux Sampling-type schemes for simulating rare events: Efficiency analysis
• Ice Nucleation on Carbon Surface Supports the Classical Theory for Heterogeneous Nucleation
• Local order parameters for use in driving homogeneous ice nucleation with all-atom models of water
• Computing stationary distributions in equilibrium and non-equilibrium systems with Forward Flux Sampling
• Microscopic Mechanism and Kinetics of Ice Formation at Complex Interfaces: Zooming in on Kaolinite
• Suppression of Sub-surface Freezing in Free-Standing Thin Films of a Coarse-grained Model of Water
• Nucleation pathway and kinetics of phase-separating active Brownian particles
• Computational investigation of structure, dynamics and nucleation kinetics of a family of modified Stillinger-Weber model fluids in bulk and free-standing thin films
• Harmonic Measure for Percolation and Ising Clusters Including Rare Events
• The Harmonic Measure for critical Potts clusters

Cited by in corpus (15)

• Thermodynamically Driven Assemblies and Liquid-liquid Phase Separations in Biology
• Unravelling the Origins of Ice Nucleation on Organic Crystals
• Induced Charge Anisotropy: a Hidden Variable Affecting Ion Transport through Membranes
• Role of Nanoscale Interfacial Proximity in Contact Freezing in Water
• How to quantify and avoid finite size effects in computational studies of crystal nucleation: The case of homogeneous crystal nucleation
• Brute-force nucleation rates of hard spheres compared with rare-event methods and classical nucleation theory
• Thermodynamics and kinetics of crystallisation in deeply supercooled Stillinger-Weber silicon
• Enhanced path sampling using subtrajectory Monte Carlo moves
• Ideal Conductor Model: An analytical finite-size correction for non-equilibrium molecular dynamics simulations of ion transport through nanoporous membranes
• Extending and validating bubble nucleation rate predictions in a Lennard-Jones fluid with enhanced sampling methods and transition state theory
• Calculation of Critical Nucleation Rates by the Persistent Embryo Method: Application to Quasi Hard Sphere Models
• Can molecular simulations reliably compare homogeneous and heterogeneous ice nucleation?
• The Impact of Hydration Shell Inclusion and Chain Exclusion in the Efficacy of Reaction Coordinates for Homogeneous and Heterogeneous Ice Nucleation
• Kinetic reconstruction of free energies as a function of multiple order parameters
• Robustness of classical nucleation theory to chemical heterogeneity of crystal nucleating substrates