Local hardness equalization: Exploiting the ambiguity
Local hardness equalization: Exploiting the ambiguity
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DOI：
10.1063/1.2918731
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发表时间：
2008-05-14
影响因子：
4.4
通讯作者：
Parr, Robert G.
中科院分区：
文献类型：
--
作者：
Ayers, Paul W.;Parr, Robert G.
在化学反应性的密度泛函理论中，局部硬度是一个模糊的概念。阐述了与这种问题情况相关的数学结构，并严格检查了局部硬度的三种常见定义：前沿局部硬度[S。K. Ghosh，Chem.Phys.Lett. 172，77（1990）]、总局部硬度[S. K. Ghosh和M. Berkowitz，J.Chem.Phys.83，2976（1985）]和无约束局部硬度[P.W. Ayers和R. G. Parr，J. Am. 122，2010（2000）]。前沿局部硬度具有特别好的性质：（a）它具有比大多数（如果不是全部）局部硬度的其他选择更小的范数，以及（B）它在信息论意义上是“无偏的”。对于分子系统的基态，前线局部硬度等于整体硬度。对于处于基态的电子系统，化学势和前沿局部硬度都是相等的。前沿局部硬度均衡原理为设计具有理想化学反应性的试剂提供了一种计算方法。(C)2008年美国物理学会。
In the density-functional theory of chemical reactivity, the local hardness is known to be an ambiguous concept. The mathematical structure associated with this problematic situation is elaborated and three common definitions for the local hardness are critically examined: the frontier local hardness [S. K. Ghosh, Chem. Phys. Lett. 172, 77 (1990)], the total local hardness [S. K. Ghosh and M. Berkowitz, J. Chem. Phys. 83, 2976 (1985)], and the unconstrained local hardness [P. W. Ayers and R. G. Parr, J. Am. Chem. Soc. 122, 2010 (2000)]. The frontier local hardness has particularly nice properties: (a) it has smaller norm than most, if not all, other choices of the local hardness and (b) it is "unbiased" in an information-theoretic sense. For the ground electronic state of a molecular system, the frontier local hardness is equal to the global hardness. For an electronic system in its ground state, both the chemical potential and the frontier local hardness are equalized. The frontier local hardness equalization principle provides a computational approach for designing reagents with desirable chemical reactivity profiles. (C) 2008 American Institute of Physics.