Automated reaction path search calculations of spin-inversion mechanisms in the 6,4,2Nb + C2H4 reaction

被引：11

作者：

Kawano, Masahiro ^{[1
]}

Koido, Shoichi ^{[1
]}

Nakatomi, Taiki ^{[1
]}

Watabe, Yuya ^{[1
]}

Takayanagi, Toshiyuki ^{[1
]}

机构：

[1] Saitama Univ, Dept Chem, Sakura Ku, Shimo Okubo 255, Saitama, Saitama 3388570, Japan

来源：

COMPUTATIONAL AND THEORETICAL CHEMISTRY | 2019年 / 1155卷

关键词：

Spin-forbidden reaction; Intersystem crossing; Spin-inversion; Transition metal; Reaction mechanism; POTENTIAL-ENERGY SURFACES; TRANSITION-STATE; CHEMICAL-REACTIONS; METAL ATOMS; KINETICS; FORMALDEHYDE; EXPLORATION; ACTIVATION; PREDICTION; COMPLEXES;

D O I：

10.1016/j.comptc.2019.03.021

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 mechanisms of C-H bond activation in C2H4 by Nb-6,Nb-4,Nb-2 metal atom have been systematically investigated using the automated reaction path search calculation with the mixed-spin Hamiltonian model. It is found that the most stable (NbC2H2)-Nb-4 + H-2 products are formed from the Nb-6 + C2H4 reactants on the sextet, quartet, and double potential energy surfaces via multiple spin-inversion (intersystem crossing) points, which are mostly associated with hydrogen atom transfer. The spin-inversion mechanisms have been further investigated by analyzing the crossing behaviors of the potential energy profiles with different spin multiplicities. We also discuss the importance of multidimensional effects on the spin-inversion dynamics.

引用

页码：31 / 37

页数：7

共 47 条

[21] Reaction mechanism of cyanoethynyl radical (C3N) with ethylene (C2H4) to form C5H3N and H: a theoretical investigation
Jiwon Moon
Joonghan Kim
Theoretical Chemistry Accounts, 2017, 136
[22] Direct Trace Fitting of Experimental Data Using the Master Equation: Testing Theory and Experiments on the OH + C2H4 Reaction
Medeiros, D. J.
Robertson, S. H.
Blitz, M. A.
Seakins, P. W.
JOURNAL OF PHYSICAL CHEMISTRY A, 2020, 124 (20) : 4015 - 4024
[23] Reactions of Aryl 5-substituted-2-Thiophenecarboxylates Promoted by 4-Z-C6H4O-/4-Z-C6H4OH in 20 mol % DMSO(aq). Effect of Nucleophile on Acyl-Transfer Reaction
Pyun, Sang Yong
Paik, Kyu Cheol
Han, Man So
Cho, Bong Rae
BULLETIN OF THE KOREAN CHEMICAL SOCIETY, 2015, 36 (12) : 2810 - 2814
[24] Ab initio study of the reaction mechanism between NH2((X)over-tilde2B1) and C2H4
Yang, GH
Zhang, HX
Tang, AQ
ACTA CHIMICA SINICA, 2001, 59 (04) : 486 - 491
[25] Synthesis of Mo(CO)2(η3-PPh2(o-C6H4)C(=O)H)2 and its reaction with C60
Chen, Chi-Shian
Lin, Cha-Shie
Yeh, Wen-Yann
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2011, 696 (07) : 1474 - 1478
[26] Effect of Thiourea on the Kinetics of the Hydrogen Evolution Reaction at Iron and the Transport of Hydrogen through a Steel Membrane in Solutions of C2H4(OH)2-H2O-HCl
V. I. Vigdorovich
L. E. Tsygankova
O. V. Alekhina
T. P. D'yachkova
Russian Journal of Electrochemistry, 2005, 41 : 1046 - 1052
[27] Reaction mechanism of CH3M≡MCH3 (M=C, Si, Ge) with C2H4: [2+1] or [2+2] cycloaddition?
Suhong Huo
Xiaoyan Li
Yanli Zeng
Shijun Zheng
Lingpeng Meng
Journal of Molecular Modeling, 2013, 19 : 3501 - 3506
[28] Effect of thiourea on the kinetics of the hydrogen evolution reaction at iron and the transport of hydrogen through a steel membrane in solutions of C2H4(OH)2-H2O-HCl
Vigdorovich, VI
Tsygankova, LE
Alekhina, OV
D'yachkova, TP
RUSSIAN JOURNAL OF ELECTROCHEMISTRY, 2005, 41 (10) : 1046 - 1052
[29] Reaction mechanism of CH3Maparts per thousandMCH3 (M=C, Si, Ge) with C2H4: [2+1] or [2+2] cycloaddition?
Huo, Suhong
Li, Xiaoyan
Zeng, Yanli
Zheng, Shijun
Meng, Lingpeng
JOURNAL OF MOLECULAR MODELING, 2013, 19 (09) : 3501 - 3506
[30] Hydrogen Scrambling in [(C5R5)(L)M(H)(C2H4)]+ (M = Co, Rh). Relation of Experimental Kinetic Data to the Barriers of the Elementary Reaction Steps
Xu, Rong
Klatt, Guenter
Wadepohl, Hubert
Koeppel, Horst
INORGANIC CHEMISTRY, 2010, 49 (07) : 3289 - 3296

← 1 2 3 4 5 →