Grand and semi-grand canonical basin-hopping
Journal of Chemical Theory and Computation
American Chemical Society
MetadataShow full item record
Calvo, F., Schebarchov, D., & Wales, D. (2015). Grand and semi-grand canonical basin-hopping. Journal of Chemical Theory and Computation, 12 902-909. https://doi.org/10.1021/acs.jctc.5b00962
We introduce grand and semi-grand canonical global optimisation approaches using basin-hopping with an acceptance criterion based on the local contribution of each potential energy minimum to the (semi-)grand potential. The method is tested using local harmonic vibrational densities of states for atomic clusters as a function of temperature and chemical potential. The predicted global minima switch from dissociated states to clusters for larger values of the chemical potential and lower temperatures, in agreement with the predictions of a model fitted to heat capacity data for selected clusters. Semi-grand canonical optimisation allows us to identify particularly stable compositions in multicomponent nanoalloys as a function of increasing temperature, while the grand canonical potential can produce a useful survey of favourable structures as a byproduct of the global optimisation search.
FC acknowledges generous computational resources granted by the regional Pôle Scientifique de Modélisation Numérique in Lyon. DJW and DS acknowledge financial support from the EPSRC and the ERC.
Embargo Lift Date
External DOI: https://doi.org/10.1021/acs.jctc.5b00962
This record's URL: https://www.repository.cam.ac.uk/handle/1810/253080
Attribution 2.0 UK: England & Wales
Licence URL: http://creativecommons.org/licenses/by/2.0/uk/