Electronic subshell splitting controls the atomic structure of charged and neutral silver clusters

Autor:	Arthur C. Reber, Shiv N. Khanna, Gabriel U. Gamboa
Rok vydání:	2013
Předmět:	Free electron model Valence (chemistry) Chemistry chemistry.chemical_element General Chemistry Prolate spheroid Electronic structure Oxygen Catalysis Formalism (philosophy of mathematics) Oblate spheroid Physics::Atomic and Molecular Clusters Materials Chemistry Atomic physics Valence electron
Zdroj:	New Journal of Chemistry. 37:3928
ISSN:	1369-9261 1144-0546
DOI:	10.1039/c3nj01075a
Popis:	Theoretical studies on the atomic and electronic structure of Agn−,0,+ clusters containing up to 15 atoms have been carried out using a gradient corrected density functional formalism. Our studies indicate that the atomic structures of the clusters undergo a transition from spherical to prolate to oblate shapes as a function of the number of valence electrons. Clusters with a valence count of 8 are shown to be highly stable and their stability is rooted in the filled 1S, 1P shells within a confined spherical nearly free electron gas. Clusters with 14 valence electrons are also shown to be highly stable, but their stability arises due to oblate geometrical distortions that lead to a splitting of the 1D shell with a large HOMO–LUMO gap. The large splitting is shown to account for the observed unusual inertness of these clusters in reactivity with oxygen. The theoretical findings are compared with the observed peaks in the photodetachment spectrum of the anionic species.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::4f28fdbd2a44d05e6ef1a2e1c658724b https://doi.org/10.1039/c3nj01075a Zobrazit plný text záznamu