Benchmark Calculations of Energetic Properties of Groups 4 and 6 Transition Metal Oxide Nanoclusters Including Comparison to Density Functional Theory

详细信息    查看全文

• 作者：Zongtang Fang ; Johan Both ; Shenggang Li ; Shuwen Yue ; Edoardo Aprà ; Murat Keçeli ; Albert F. Wagner ; David A. Dixon
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2016
• 出版时间：August 9, 2016
• 年：2016
• 卷：12
• 期：8
• 页码：3689-3710
• 全文大小：874K
• 年卷期：0
• ISSN：1549-9626

文摘

The heats of formation and the normalized clustering energies (NCEs) for the group 4 and group 6 transition metal oxide (TMO) trimers and tetramers have been calculated by the Feller–Peterson–Dixon (FPD) method. The heats of formation predicted by the FPD method do not differ much from those previously derived from the NCEs at the CCSD(T)/aT level except for the CrO₃ nanoclusters. New and improved heats of formation for Cr₃O₉ and Cr₄O₁₂ were obtained using PW91 orbitals instead of Hartree-Fock (HF) orbitals. Diffuse functions are necessary to predict accurate heats of formation. The fluoride affinities (FAs) are calculated with the CCSD(T) method. The relative energies (REs) of different isomers, NCEs, electron affinities (EAs), and FAs of (MO₂)_n (M = Ti, Zr, Hf, n = 1–4) and (MO₃)_n (M = Cr, Mo, W, n = 1–3) clusters have been benchmarked with 55 exchange-correlation density functional theory (DFT) functionals including both pure and hybrid types. The absolute errors of the DFT results are mostly less than ±10 kcal/mol for the NCEs and the EAs and less than ±15 kcal/mol for the FAs. Hybrid functionals usually perform better than the pure functionals for the REs and NCEs. The performance of the two types of functionals in predicting EAs and FAs is comparable. The B1B95 and PBE1PBE functionals provide reliable energetic properties for most isomers. Long range corrected pure functionals usually give poor FAs. The standard deviation of the absolute error is always close to the mean errors, and the probability distributions of the DFT errors are often not Gaussian (normal). The breadth of the distribution of errors and the maximum probability are dependent on the energy property and the isomer.