Structural changes of Pd-13 upon charging and oxidation/reduction

Authors

J. Ulises Reveles, Virginia Commonwealth UniversityFollow
A. M. Köster, Avenida Instituto Politecnico Nacional
P. Calaminici, Avenida Instituto Politecnico Nacional
S. N. Khanna, Virginia Commonwealth UniversityFollow

Document Type

Article

Original Publication Date

2012

Journal/Book/Conference Title

The Journal of Chemical Physics

Volume

136

Issue

11

DOI of Original Publication

10.1063/1.3692612

Comments

Originally published at https://dx.doi.org/10.1063/1.3692612

Date of Submission

October 2015

Abstract

First-principle generalized gradient corrected density functional calculations have been performed to study the stability of cationic and anionic Pd₁₃ ^+/−, and neutral Pd₁₃O₂ clusters. It is found that while cationic Pd₁₃ ⁺ favors a C _s geometry similar to the neutral Pd₁₃, both anionic Pd₁₃ ⁻ and neutral Pd₁₃O₂ 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 Pd₁₃ in which small energy barriers between 0.3 and 0.4 eV are involved.

Rights

Reveles, J. U., Koster, A. M., & Calaminici, P., et al. Structural changes of Pd-13 upon charging and oxidation/reduction. The Journal of Chemical Physics, 136, 114505 (2012). Copyright © 2012 American Institute of Physics.

Is Part Of

VCU Physics Publications