eprintid: 123680 rev_number: 43 eprint_status: archive userid: 608 dir: disk0/00/12/36/80 datestamp: 2010-10-23 16:52:02 lastmod: 2021-11-01 02:03:38 status_changed: 2015-12-15 11:39:15 type: article metadata_visibility: show item_issues_count: 0 creators_name: Ford, IJ creators_name: Harris, SA title: Molecular cluster decay viewed as escape from a potential of mean force ispublished: pub divisions: UCL divisions: B04 divisions: C06 divisions: F60 keywords: Monte-Carlo-simulation, homogeneous nucleation rate, vapor-liquid nucleation, physical clusters, equilibrium, definition, transition, gases, water note: © 2004 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in Ford, IJ; Harris, SA; (2004) Molecular cluster decay viewed as escape from a potential of mean force. Journal of Chemical Physics , 120 (9) 4428 - 4440. and may be found at http://dx.doi.org/10.1063/1.1644533. abstract: We show that evaporation from a quasistable molecular cluster may be treated as a kinetic problem involving the stochastically driven escape of a molecule from a potential of mean force. We derive expressions for the decay rate, and a relationship between the depth of the potential and the change in system free energy upon loss of a molecule from the cluster. This establishes a connection between kinetic and thermodynamic treatments of evaporation, but also reveals differences in the prefactor in the rate expression. We perform constant energy molecular dynamics simulations of cluster dynamics to calculate potentials of mean force, friction coefficients and effective temperatures for use in the kinetic analysis, and to compare the results with the directly observed escape rates. We also use the simulations to estimate the escape rates by a probabilistic analysis. It is much more efficient to calculate the decay rate by the methods we have developed than it is to monitor escape directly, making these approaches potentially useful for the assessment of molecular cluster stability. (C) 2004 American Institute of Physics. date: 2004-03-01 publisher: AMER INST PHYSICS official_url: http://dx.doi.org/10.1063/1.1644533 vfaculties: VMPS oa_status: green full_text_type: other language: eng primo: open primo_central: open_green article_type_text: Article verified: verified_manual elements_source: Web of Science elements_id: 48915 doi: 10.1063/1.1644533 language_elements: EN lyricists_name: Ford, Ian lyricists_id: IJFOR04 full_text_status: public publication: Journal of Chemical Physics volume: 120 number: 9 pagerange: 4428 - 4440 issn: 0021-9606 citation: Ford, IJ; Harris, SA; (2004) Molecular cluster decay viewed as escape from a potential of mean force. Journal of Chemical Physics , 120 (9) 4428 - 4440. 10.1063/1.1644533 <https://doi.org/10.1063/1.1644533>. Green open access document_url: https://discovery.ucl.ac.uk/id/eprint/123680/7/Ford_escapepaper2.pdf