Benchmarking Density Functional Theory Based Methods To Model NiOOH Material Properties: Hubbard and van der Waals Corrections vs Hybrid Functionals

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• 作者：Jeremie Zaffran ; Maytal Caspary Toroker
• 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：3807-3812
• 全文大小：373K
• 年卷期：0
• ISSN：1549-9626

文摘

NiOOH has recently been used to catalyze water oxidation by way of electrochemical water splitting. Few experimental data are available to rationalize the successful catalytic capability of NiOOH. Thus, theory has a distinctive role for studying its properties. However, the unique layered structure of NiOOH is associated with the presence of essential dispersion forces within the lattice. Hence, the choice of an appropriate exchange-correlation functional within Density Functional Theory (DFT) is not straightforward. In this work, we will show that standard DFT is sufficient to evaluate the geometry, but DFT+U and hybrid functionals are required to calculate the oxidation states. Notably, the benefit of DFT with van der Waals correction is marginal. Furthermore, only hybrid functionals succeed in opening a bandgap, and such methods are necessary to study NiOOH electronic structure. In this work, we expect to give guidelines to theoreticians dealing with this material and to present a rational approach in the choice of the DFT method of calculation.