Toward the construction of parameter‐free doubly hybrid density functionals
Toward the construction of parameter‐free doubly hybrid density functionals
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DOI：
10.1002/qua.24849
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发表时间：
2015-05
影响因子：
2.2
通讯作者：
N. Su;Xin Xu
中科院分区：
文献类型：
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作者：
N. Su;Xin Xu
双杂化泛函提出了一类新的密度泛函，它不仅将非定域轨道相关成分包含在交换部分，而且也包含在关联部分。根据不同的哲学思想，人们提出了不同类型的水解式泛函。结果表明，与其他常规泛函相比，DH泛函能更好地满足某些物理条件，如分数电荷的线性条件，这解释了它在描述主族化学的热化学和热化学动力学方面的普遍改进。应努力构造无参数的dH泛函，并正确描述具有强静态相关性的离解极限。后者与分数自旋误差有关，减小分数自旋误差对于过渡金属化学的安全应用具有重要意义。©2014 Wiley期刊，Inc.
Doubly hybrid (DH) functionals present a new class of density functionals, which enfold the nonlocal orbital-dependent components not only in the exchange part but also in the correlation part. Different types of DH functionals have been proposed according to different philosophies. DH functionals are shown to better fulfill certain physical conditions such as the linearity condition for fractional charges than other conventional functionals, which accounts for the generally improved performances of DH functionals in the description of thermochemistry and thermochemical kinetics for the main group chemistry. Efforts shall be made toward the construction of parameter-free DH functionals and the proper description of the dissociation limit with strong static correlation. The latter is related to the fractional spin errors, the reduction of which is important for secure applications in transition metal chemistry. © 2014 Wiley Periodicals, Inc.