Theoretical Study on Electronic Properties and Structural Evolution in Hf2On-/0 (n=1~6) Clusters

doi:10.6023/A16090505

Abstract

Extensive density functional theoretical (DFT) and ab initio[CCSD (T)]calculations were combined to investigate the geometric and electronic structure of a series of dinuclear hafnium oxide clusters,Hf₂O_n^-/0(n=1~6).DFT calculations were performed to search for the lowest energy structures for both the anionic clusters and the neutral counterparts.The search for the global minima was performed using analytical gradients with the Stuttgart relativistic small core potential and the valence basis sets augmented with two f-type and one g-type polarization functions for Hf and the aug-cc-pVTZ basis set for oxygen.The relative energies of the low-lying structures (within ca.0.35 eV) were further evaluated via single-point calculations at the coupled cluster[CCSD (T)]level with the Hf/Stuttgart+2f1g/O/aug-cc-pVTZ basis sets at the B3LYP geometries.Generalized Koopmans' theorem (GKT) was applied to predict VDEs and simulate the anion photoelectron spectra (PES).The trends of structural evolution and the behavior of sequential oxidation of the Hf₂O_n^-(n=1~6) clusters were observed.For the anionic species,starting from the C_2v triangular structure Hf₂O^-,the next O atom in the Hf₂O₂^- cluster was again bridge-bonded,forming a rhombus structure.The third O atom occupied the terminal site.The fourth O atom favored the bridging site and the fifth O atom occupied the terminal site.In Hf₂O₆^-,the additional O atom was bonded to a terminal site.Molecular orbital analyses were performed to elucidate the chemical bonding and the structural evolution in Hf₂O_n^-(n=1~4) clusters.Spin density analyses revealed oxygen radical,diradical and superoxide characters in the oxygen-rich clusters,except for the singlet Hf₂O₅ cluster.We showed that Hf₂O₃ contains a localized Hf²⁺ site,which can readily react with O₂ to form the Hf₂O₅ cluster.The Hf₂O₆^- and Hf₂O₆ clusters,which can be viewed to be formed by the interaction of Hf₂O₄^-/0 and O₂,may be utilized as molecular models to understand dioxygen activation on Hf₂O₄^- and Hf₂O₄ clusters.

Key words: hafnium oxide cluster, DFT, CCSD (T), radical, simulated PES

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Chen Shifang, Chen Wenjie, Wang Bin, Zhang Xiaobin, Huang Xin, Zhang Yongfan. Theoretical Study on Electronic Properties and Structural Evolution in Hf₂O_n^-/0 (n=1~6) Clusters[J]. Acta Chim. Sinica, 2016, 74(12): 1009-1017.

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二核铪氧簇Hf₂O_n^-/0(n=1~6)的电子性质与结构演化的理论研究

Theoretical Study on Electronic Properties and Structural Evolution in Hf₂O_n^-/0 (n=1~6) Clusters

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二核铪氧簇Hf2On-/0(n=1~6)的电子性质与结构演化的理论研究