Abstract
The dynamic and thermodynamic properties of nanoclusters are studied in two different environments: the canonical and microcanonical ensembles. A comparison is made to thermodynamic properties of the bulk. It is shown that consistent and reproducible results on nanoclusters can only be obtained in the canonical ensemble. Nanoclusters in the microcanonical ensemble are trapped systems, and inconsistencies will be found if thermodynamic formalism is applied. An analytical model is given for the energy dependence of the phase space volume of nanoclusters, which allows the prediction of both dynamical and thermodynamical properties.
Highlights
Nanoclusters are small finite systems consisting of from several atoms to several thousands of atoms
We have studied the dynamics and thermodynamics of nanoclusters in two different environments, the canonical and the microcanonical ensembles
We have shown that equilibrium thermodynamic properties can only be obtained from the canonical ensemble and that nanoclusters in the microcanonical ensemble are trapped systems
Summary
Nanoclusters are small finite systems consisting of from several atoms to several thousands of atoms. It will become clear that the choice of the environment, or ensemble, in which the thermodynamic properties of the nanocluster are to be determined is crucial, since they generally lead to different, and inconsistent, results This is because in the microcanonical ensemble, nanoclusters inevitably become trapped at low energy in only a sub-region of the energetically-available phase space, and so, the system never arrives at a true thermodynamic equilibrium, independently of the amount of time allowed for convergence. We consider a modification of our model for the thermodynamics that allows us to include energy barriers and, to simulate what would be expected in the microcanonical ensemble for particular initial conditions This allows initial condition-dependent dynamical information to be obtained for the system.
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