Influence of Spin Multiplicity on the Melting of Na55

• Published in: The journal of physical chemistry letters Vol. 6; no. 22; pp. 4646 - 4652
• Main Authors: Vásquez-Pérez, J. M, Gamboa, G. U, Mejía-Rodríguez, D, Alvarez-Ibarra, A, Geudtner, G, Calaminici, P, Köster, A. M
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 19.11.2015
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.5b01983

The influence of spin multiplicity on the melting of the Na55 + cluster has been investigated by means of all-electron Kohn–Sham Born–Oppenheimer molecular dynamics simulations. On the basis of the quantitative agreement between the experimental and theoretical melting temperature and latent heat a detailed analysis of the cluster dynamics was performed. This analysis showed a significant structure deformation of the cluster that is inconsistent with the geometrical shell closing concept. In subsequent structure optimizations a high-spin ground state in perfect icosahedral symmetry was found for the Na55 + cluster. The Born–Oppenheimer molecular dynamics of this high-spin Na55 + cluster indicates a particular thermal stability of the icosahedral cluster structure. A new electronic mechanism, named subshell closing, is suggested as the origin for this enhanced thermal stability of the icosahedral cluster structure. This mechanism is a natural extension of the common jellium model. By its nature, the subshell closing mechanism is general for finite systems and expected to be found in many other clusters for which the jellium model is applicable.