Computational study on the molecular structures and photoelectron spectra of bimetallic oxide clusters (M=V, Nb, Ta)

Chen, Wen-Jie; Zhang, Chang-Fu; Zhang, Xian-Hui; Zhang, Yongfan; Huang, Xin

doi:10.1016/j.saa.2013.02.011

Cited by 8 publications

(1 citation statement)

References 124 publications

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“…The cluster [Ta 6 I 12 (H 2 O) 6 ] 2+ was computationally investigated at three different levels of theory: Hartree–Fock self-consistent field (HF-SCF), second-order Møller–Plesset (MP2) perturbation theory, and density functional theory (DFT). The triple-ζ Ahlrichs Def2-TZVPP basis set was used; the choice of basis set was driven by previous studies on Ta compounds. For the DFT calculations, five different exchange-correlation functions were tested: B3LYP, CAM-B3LYP, PBE0, M06-2X, and ω-B97X[D] .…”

Section: Methodsmentioning

confidence: 99%

Octahedral {Ta₆I₁₂} Clusters

et al. 2019

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Ta powder reacts with I 2 at 650 °C with the formation of Ta 6 I 14 , which belongs to the family of {M 6 (μ-X) 12 } clusters. It undergoes aquation with the formation of the intensely colored [Ta 6 I 12 (H 2 O) 6 ] 2+ . The crystal structure was determined for [Ta 6 I 12 2+ shows two consecutive quasi-reversible one-electron oxidations (E 1/2 0.61 and 0.92 V vs Ag/AgCl). Reaction of Ta 6 I 14 with Bu 4 NCN yields (Bu 4 N) 4 [Ta 6 I 12 (CN) 6 ]•xCH 3 CN (Ta−Ta 2.9777(4) Å, Ta−I 2.8165(6) Å, Ta−C 2.2730(7) Å). Quantum chemical calculations reproduce well the experimental geometry of the aqua complex and show the essentially Ta-centered nature of both the HOMO and LUMO. The long-term stability of [Ta 6 I 12 (H 2 O) 6 ] 2+ solutions can be greatly enhanced in the presence of polystyrenesulfonate (PSS), which forms nanoparticle associates with the aqua complex in water (ca. 1 cluster per 3 PSS monomeric units).

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