Structural, electronic and magnetic properties of copper(I) cubic clusters
Autor
Barboza, Cristina Aparecida
Gambetta, Adrian
Arratia-Pérez, Ramiro
Rodríguez-Kessler, P. L.
Muñoz-Castro, Alvaro
MacLeod-Carey, Desmond
Resumen
We report the molecular and electronic structure, and the calculated electronic excitation energies, using the time dependent density functional methodologies (TD-DFT), and the induced magnetic field (Bi) of a series of Cu(I) dithiolato and diselenolato species of formula [Cu8(L)6]. They are composed by eight copper atoms forming a Cu8 cube and six bidentate ligands (L), where twelve chalcogen atoms (Q) bridging the edges of the copper cube, in such a way that chalcogen atoms describe an icosahedron, enclosing a cubic [Cu8(μ-Q12)]4− core of Th symmetry. The Q…Q bite distance is similar in all clusters, without being influenced by the Cu-Cu distance, suggesting the existence of metallophilic interactions that stabilize the cluster structure. Despite of the structural similarities, the electronic structure of these clusters present some differences which are magnified on their optical properties. Excitation energies and their composition depend on the nature of each different ligand in these clusters, according to CTλ(M) index to determine the ligand to metal (LM) or metal to ligand charge transfer (MLCT) character of each calculated electronic transition. The magnetic properties calculations show the importance to separate the magnetic response into their individual components (Bi with i = x, y, z, iso), and diamagnetic and paramagnetic contributions to understand the differences according to the type of ligand on the cluster structure.
Colecciones
Ítems relacionados
Mostrando ítems relacionados por Título, autor o materia.
-
Article
Exploring the Size-Dependent Hydrogen Storage Property on Ti-Doped Bn Clusters by Diatomic Deposition: Temperature Controlled H2 Release (2021)
Rodríguez-Kessler, P. L.; Rodríguez-Domínguez, Adán R.; MacLeod-Carey, Desmond; Munõz-Castro, Alvaro (John Wiley and Sons Inc, 2021)The hydrogen storage properties of Ti-doped Bn ((Formula presented.)) clusters are investigated by using the “diatomic deposition method” with further evaluation by density functional theory computations. The results show ... -
Article
Reply to ‘Comment on “Structural characterization, reactivity, and vibrational properties of silver clusters: A new global minimum for Ag16”’ by P. V. Nhat, N. T. Si, L. V. Duong and M. T. Nguyen,Phys. Chem. Chem. Phys., 2021,23, DOI: D1CP00646K (2021)
Rodríguez-Kessler, P. L.; Rodríguez-Domínguez, Adán R.; MacLeod-Carey, Desmond; Muñoz-Castro, Alvaro (Royal Society of Chemistry, 2021-06-14)Recently, P. V. Nhatet al., have discussed and commented on our article (DOI: 10.1039/D0CP04018E) for the case of the most stable structure of Ag15. They have found a new most stable structure (labeled as 15-1) in comparison ... -
Article
Relativistic effects on dative carbon-coinage metal bond. Evaluation of NHC-MCl (M = Cu, Ag, Au) from relativistic DFT (2021)
Munõz-Castro, Alvaro; MacLeod-Carey, Desmond; Arratia-Pérez, Ramiro (Elsevier Ltd, 2021-03-15)The use of different N-heterocyclic carbene (NHC) as dative ligands benefits from their capabilities ranging from strong to weak σ-donor according to the Tolman electronic parameter (TEP), well spread in the formation of ...