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MVO-10: A Gas-Phase Oxide Benchmark for Localization/Delocalization in Mixed-Valence Systems
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2018-06-06 00:00:00 , DOI: 10.1021/acs.jctc.8b00289
Sascha Klawohn 1 , Martin Kaupp 1 , Amir Karton 2
Affiliation  

Ten simple gas-phase, main-group as well as transition-metal, mixed-valence (MV) oxo complexes are suggested for the screening of electronic-structure methods for the computational study of localization vs delocalization of charge and spin density in MV systems, without the usual added complication of environmental effects. Benchmark coupled-cluster energies up to CCSDT(Q)/CBS (for Al2O4, Si2O4+, Si2O4, ScO2, TiO2+) and CCSD(T)/CBS (for Ti2O4, Ti2O4, V2O4+, Cr2O6) quality are provided as a basis for screening a variety of density-functional methods, ranging from a generalized gradient approximation via global and range-separated to local hybrid functionals. Additionally, experimental evidence for a delocalized D2d structure of the somewhat larger V4O10 is used. None of the functionals is fully satisfactory when tasked with describing simultaneously the most extreme cases, the localized Al2O4 and the delocalized V4O10. While relatively large exact-exchange admixtures are required for the former, and for related localized cases, lower ones are preferable for the latter, as well for other delocalized d1d0 systems. The overall best combined performance is provided by a Lh-SVWN (g(r) = 0.670 τW/τ) local hybrid, the MN15 global hybrid, and the ωB97X-D range-separated hybrid. We also provide vibrational data for comparison with experiment.

中文翻译:

MVO-10:混合价系统中用于本地化/去本地化的气相氧化物基准

建议使用十种简单的气相,主族以及过渡金属,混合价(MV)氧代配合物筛选电子结构方法,以计算研究MV系统中电荷和自旋密度的局部化与离域化,而不会增加通常的环境影响的复杂性。基准耦合簇能量高达CCSDT(Q)/ CBS(对于Al 2 O 4 ,Si 2 O 4 +,Si 2 O 4 ,ScO 2,TiO 2 +)和CCSD(T)/ CBS(对于Ti 2 O 4 ,Ti 2 O 4 ,V 2 O 4 +,Cr 2 O 6 )的质量是筛选各种密度泛函方法的基础,从通过全局和范围分离的广义梯度近似到局部混合泛函,范围广泛。此外,还使用了较大的V 4 O 10 的离域D 2d结构的实验证据。当要同时描述最极端的情况时,没有一种功能是完全令人满意的,局部的Al 2 O 4 和离域的V 4 O 10 。尽管前者和相关的局部情况需要相对较大的精确交换混合物,但后者和其他非局域化d 1 d 0系统则需要较低的精确交换混合物。整体最佳综合性能是由LH-SVWN提供(克([R)= 0.670τ w ^ /τ)局部混合时,MN15全球混合,并且ωB97X-d范围分隔的混合体。我们还提供振动数据,以便与实验进行比较。
更新日期:2018-06-06
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