DFT, DLPNO‐CCSD(T), and NEVPT2 benchmark study of the reaction between ferrocenium and trimethylphosphine
DFT, DLPNO‐CCSD(T), and NEVPT2 benchmark study of the reaction between ferrocenium and trimethylphosphine
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二茂铁与三甲基膦反应的 DFT、DLPNO-CCSD(T) 和 NEVPT2 基准研究
DOI：
10.1002/jcc.26398
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发表时间：
2020
影响因子：
3
通讯作者：
E. Serkova
中科院分区：
文献类型：
--
作者：
A. Chamkin;E. Serkova
采用密度泛函理论（DFT）、单激发、双激发和微扰三重激发的局域对自然轨道耦合簇理论（DLPNO-CCSD（T））和N电子价态微扰理论（NEVPT 2）研究了二茂铁与三甲基膦的反应.与DLPNO-CCSD（T）水平相比，DFT泛函的准确性按以下顺序降低：M06-L > TPSS > M06，BLYP > PBE，PBE 0，B3 LYP> > PWPB 95> > DSD-BLYP。热化学，连续溶剂化（SMD），和平衡校正的作用进行了评价。格里姆的D3经验色散校正对于除了M06和M06-L之外的所有泛函都是必不可少的。在SMD内直接进行的频率计算的可靠性得到了证实。根据T1和T2诊断和分数占据数（FOD）加权电子密度分析，系统未显示出显著的多参考特征。多参考NEVPT 2计算给出了反应机理的定性有效的结论。但是，通常不建议使用多引用方法，因为它需要任意选择活动空间。
The reaction between ferrocenium and trimethylphosphine was studied using density functional theory (DFT), domain‐based local pair natural orbital coupled cluster theory with single‐, double‐, and perturbative triple excitations (DLPNO‐CCSD(T)), and N‐electron valence state perturbation theory (NEVPT2). The accuracy of the DFT functionals decreases compared to the DLPNO‐CCSD(T) level in the following order: M06‐L > TPSS > M06, BLYP > PBE, PBE0, B3LYP > > PWPB95 > > DSD‐BLYP. The roles of thermochemical, continuum solvation (SMD), and counterpoise corrections were evaluated. Grimme's D3 empirical dispersion correction is essential for all functionals studied except M06 and M06‐L. The reliability of the frequency calculations performed directly within the SMD was confirmed. The systems showed no significant multireference character according to T1 and T2 diagnostics and the fractional occupation number (FOD) weighted electron density analysis. The multireference NEVPT2 calculations gave qualitatively valid conclusions about the reaction mechanism. However, a multireference approach is generally not recommended because it requires arbitrary chosen active spaces.
DOI：
10.1063/1.4981521
发表时间：
2017-04
期刊：
The Journal of chemical physics
影响因子：
--
作者：
Masaaki Saitow;Ute Becker;Christoph Riplinger;Edward F. Valeev;F. Neese
通讯作者：
Masaaki Saitow;Ute Becker;Christoph Riplinger;Edward F. Valeev;F. Neese
影响因子：
5.5
作者：
Wheeler, Steven E.;Houk, K. N.
通讯作者：
Houk, K. N.