Computational Studies on Ethylene Addition to Nickel Bis(dithiolene)

被引：37

作者：

Dang, Li ^{[2
]}

Yang, Xinzheng ^{[2
]}

Zhou, Jia ^{[2
]}

Brothers, Edward N. ^{[1
]}

Hall, Michael B. ^{[2
]}

机构：

[1] Texas A&M Univ Qatar, Dept Chem, Doha, Qatar

[2] Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2012年 / 116卷 / 01期

关键词：

GAUSSIAN-BASIS SETS; QUADRATIC CONFIGURATION-INTERACTION; CORRELATED MOLECULAR CALCULATIONS; 2ND-ORDER PERTURBATION-THEORY; COUPLED-CLUSTER SINGLES; DENSITY FUNCTIONALS; ELECTRONIC-STRUCTURE; WAVE-FUNCTIONS; OXIDATIVE CYCLOADDITION; MODEL CHEMISTRY;

D O I：

10.1021/jp205971b

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The density functionals B3LYP, B3PW91, BMK, HSE06, LC-omega PBE, M05, M06, O3LYP, TPSS, omega-B97X, and omega-B97XD are used to optimize key transition states and intermediates for ethylene addition to Ni(edt)(2) (edt = S2C2H2). The efficacy of the basis sets 6-31G**, 6-31++G**, cc-pVDZ, aug-cc-pVDZ, cc-pVTZ, and aug-cc-pVTZ is also examined; The geometric parameters optimized with different basis sets and density functionals are similar and agree well with experimental values. The omega-B97XD functional gives relative energies closest to those from CCSD, while M06 and HSE06 yield results close to those from CCSD(T). CASSCF and CASSCF-PT2 calculation results are also given. Variation of the relative energies from different density functionals appears to arise, in part, from the multireference character of this system, as confirmed by the T1 diagnostic and CASSCF calculations.

引用

页码：476 / 482

页数：7

共 101 条

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