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.
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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.
| Type: | Article |
|---|---|
| Title: | Molecular cluster decay viewed as escape from a potential of mean force |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1063/1.1644533 |
| Publisher version: | http://dx.doi.org/10.1063/1.1644533 |
| Language: | English |
| Additional information: | © 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. |
| Keywords: | Monte-Carlo-simulation, homogeneous nucleation rate, vapor-liquid nucleation, physical clusters, equilibrium, definition, transition, gases, water |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy |
| URI: | https://discovery.ucl.ac.uk/id/eprint/123680 |
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