Structure and Electronic Properties of Neutral and Negatively Charged RhBn Clusters (n = 3–10): A Density Functional Theory Study
| Autor: | Peifang Li, Gang Bao, Weihua Wang, Gennady L. Gutsev, Tingting Mei, Linxia Lv, Cheng Lu |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
Chemistry
Binding energy 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Potential energy Spectral line 0104 chemical sciences Delocalized electron Chemical bond Physics::Atomic and Molecular Clusters Cluster (physics) Density functional theory Physical and Theoretical Chemistry Atomic physics 0210 nano-technology Basis set |
| Zdroj: | The Journal of Physical Chemistry A. 121:6510-6516 |
| ISSN: | 1520-5215 1089-5639 |
| Popis: | The geometrical structure and electronic properties of the neutral RhBn and singly negatively charged RhBn- clusters are obtained in the range of 3 ≤ n ≤ 10 using the unbiased CALYPSO structure search method and density functional theory (DFT). A combination of the PBE0 functional and the def2-TZVP basis set is used for determining global minima on potential energy surfaces of the Rh-doped Bn clusters. The photoelectron spectra of the anions are simulated using the time-dependent density functional theory (TD-DFT) method. Good agreement between our simulated and experimentally obtained photoelectron spectra for RhB9- provides support to the validity of our theoretical method. The relative stabilities of the ground-state RhBn and RhBn- clusters are estimated using the calculated binding energies, second-order total energy differences, and HOMO-LUMO gaps. It is found that RhB7 and RhB8- are the most stable species in the neutral and anionic series, respectively. The chemical bonding analysis reveals that the RhB8-cluster possesses two sets of delocalized σ and π bonds. In both cases, the Huckel 4N + 2 rule is fulfilled and this cluster possesses both σ and π aromaticities. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|