Richard Adrien, Corà Furio
Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.
J Phys Chem C Nanomater Interfaces. 2023 May 26;127(22):10766-10776. doi: 10.1021/acs.jpcc.3c01013. eCollection 2023 Jun 8.
The accurate determination of relative phase stabilities using DFT methods is a significant challenge when some of these can vary by only a few kJ/mol. Here, we demonstrate that for a selection of oxides (TiO, MnO, and ZnO) the inclusion of dispersion interactions, accomplished using the DFT-D3 correction scheme, allows for the correct ordering and an improved calculation of the energy differences between polymorphic phases. The energetic correction provided is of the same order of magnitude as the energy difference between phases. D3-corrected hybrid functionals systematically yield results closest to experiment. We propose that the inclusion of dispersion interactions makes a significant contribution to the relative energetics of polymorphic phases, especially those with different densities, and should therefore be included for calculations of relative energies using DFT methods.
当其中一些相对相稳定性仅相差几kJ/mol时，使用密度泛函理论（DFT）方法准确确定相对相稳定性是一项重大挑战。在这里，我们证明，对于选定的几种氧化物（TiO、MnO和ZnO），采用DFT-D3校正方案纳入色散相互作用，能够实现正确的排序，并改进多晶型相之间能量差的计算。所提供的能量校正与相之间的能量差具有相同的数量级。经D3校正的杂化泛函系统地产生最接近实验结果的结果。我们提出，纳入色散相互作用对多晶型相的相对能量学有重大贡献，尤其是那些具有不同密度的相，因此在使用DFT方法计算相对能量时应予以考虑。
