title: Structural changes of Pd13 upon charging and oxidation/reduction.
abstract: First-principle generalized gradient corrected density functional calculations have been performed to study the stability of cationic and anionic Pd(13) (+∕-), and neutral Pd(13)O(2) clusters. It is found that while cationic Pd(13) (+) favors a C(s) geometry similar to the neutral Pd(13), both anionic Pd(13)(-) and neutral Pd(13)O(2) favor a compact ~I(h) structure. A detailed analysis of the electronic structure shows that the stabilization of the delocalized 1P and 2P cluster orbitals, and the hybridization of the 1D orbitals with the oxygen atomic p orbitals play an important role in the energetic ordering of C(s) and ~I(h) isomers. A structural oscillation is predicted during an oxidation/reduction cycle of Pd(13) in which small energy barriers between 0.3 and 0.4 eV are involved.
authors.affiliation: Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284-2000, USA. jureveles@vcu.edu
authors.forename: J Ulises
authors.initials: JU
authors.lastname: Reveles
authors.forename: A M
authors.initials: AM
authors.lastname: Köster
authors.forename: P
authors.initials: P
authors.lastname: Calaminici
authors.forename: S N
authors.initials: SN
authors.lastname: Khanna