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从正戊烷的构象表面我们可以了解到什么关于离域的信息?

What can we learn about dispersion from the conformer surface of n-pentane?

机构信息

Department of Chemistry and Center for Advanced Scientific Computing and Modeling (CASCaM), University of North Texas, Denton, Texas 76201, USA.

出版信息

J Phys Chem A. 2013 Apr 11;117(14):3118-32. doi: 10.1021/jp401429u. Epub 2013 Mar 28.

DOI:10.1021/jp401429u
PMID:23452230
Abstract

In earlier work [Gruzman, D. ; Karton, A.; Martin, J. M. L. J. Phys. Chem. A 2009, 113, 11974], we showed that conformer energies in alkanes (and other systems) are highly dispersion-driven and that uncorrected DFT functionals fail badly at reproducing them, while simple empirical dispersion corrections tend to overcorrect. To gain greater insight into the nature of the phenomenon, we have mapped the torsional surface of n-pentane to 10-degree resolution at the CCSD(T)-F12 level near the basis set limit. The data obtained have been decomposed by order of perturbation theory, excitation level, and same-spin vs opposite-spin character. A large number of approximate electronic structure methods have been considered, as well as several empirical dispersion corrections. Our chief conclusions are as follows: (a) the effect of dispersion is dominated by same-spin correlation (or triplet-pair correlation, from a different perspective); (b) singlet-pair correlation is important for the surface, but qualitatively very dissimilar to the dispersion component; (c) single and double excitations beyond third order are essentially unimportant for this surface; (d) connected triple excitations do play a role but are statistically very similar to the MP2 singlet-pair correlation; (e) the form of the damping function is crucial for good performance of empirical dispersion corrections; (f) at least in the lower-energy regions, SCS-MP2 and especially MP2.5 perform very well; (g) novel spin-component scaled double hybrid functionals such as DSD-PBEP86-D2 acquit themselves very well for this problem.

摘要

在早期的工作中[Gruzman, D. ; Karton, A.; Martin, J. M. L. J. Phys. Chem. A 2009, 113, 11974],我们表明烷烃(和其他系统)中的构象能高度依赖于色散,而未经修正的 DFT 泛函在重现它们时表现得非常差,而简单的经验色散校正往往会过度校正。为了更深入地了解这一现象的本质,我们在 CCSD(T)-F12 水平上,在基组极限附近,以 10 度的分辨率对正戊烷的扭转表面进行了映射。通过微扰理论、激发水平和同自旋与反自旋特性的顺序对获得的数据进行了分解。我们考虑了大量的近似电子结构方法,以及几种经验色散校正。我们的主要结论如下:(a)色散的影响主要由同自旋相关(或从另一个角度看,三重态对相关)决定;(b)单重态相关对表面很重要,但在质上与色散分量非常不同;(c)三阶以上的单重和双重激发对这个表面基本上不重要;(d)连接三重激发确实起作用,但在统计学上与 MP2 单重态相关非常相似;(e)阻尼函数的形式对于经验色散校正的良好性能至关重要;(f)至少在较低能量区域,SCS-MP2 特别是 MP2.5 表现得非常好;(g)新型的自旋分量缩放双杂化泛函,如 DSD-PBEP86-D2,在这个问题上表现得非常出色。

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