Deformed Transition-State Theory: Deviation from Arrhenius Behavior and Application to Bimolecular Hydrogen Transfer Reaction Rates in the Tunneling Regime

被引:48
作者
Carvalho-Silva, Valter H. [1 ]
Aquilanti, Vincenzo [2 ,3 ,4 ]
de Oliveira, Heibbe C. B. [5 ]
Mundim, Kleber C. [5 ]
机构
[1] Univ Estadual Goias, Unidade Univ Ciencias Exatas & Tecnol, Grp Quimica Teorica & Estrutural Anapolis, POB 459, BR-75001970 Anapolis, Go, Brazil
[2] Univ Perugia, Dipartimento Chim Biol & Biotecnol, Via Elce Sotto 8, I-06123 Perugia, Italy
[3] Univ Fed Bahia, Inst Fis, BR-40210 Salvador, BA, Brazil
[4] CNR, Ist Struttura Mat, I-00016 Rome, Italy
[5] Univ Brasilia, Inst Quim, Caixa Postal 4478, I-70904970 Brasilia, DF, Brazil
关键词
non-Arrhenius; sub-Arrhenius; d-Arrhenius; transition-state theory; hydrogen transfer; GAS-PHASE REACTIONS; RATE CONSTANTS; TEMPERATURE-DEPENDENCE; MOLECULAR-DYNAMICS; CHEMICAL-KINETICS; RATE COEFFICIENT; FALSE VACUUM; AB-INITIO; HYDROXYL; ENERGY;
D O I
10.1002/jcc.24529
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A formulation is presented for the application of tools from quantum chemistry and transition-state theory to phenomenologically cover cases where reaction rates deviate from Arrhenius law at low temperatures. A parameter d is introduced to describe the deviation for the systems from reaching the thermodynamic limit and is identified as the linearizing coefficient in the dependence of the inverse activation energy with inverse temperature. Its physical meaning is given and when deviation can be ascribed to quantum mechanical tunneling its value is calculated explicitly. Here, a new derivation is given of the previously established relationship of the parameter d with features of the barrier in the potential energy surface. The proposed variant of transition state theory permits comparison with experiments and tests against alternative formulations. Prescriptions are provided and implemented to three hydrogen transfer reactions: CH4 + OH -> CH3 + H2O, CH3Cl + OH -> CH2Cl + H2O and H-2 + CN -> H + HCN, widely investigated both experimentally and theoretically. (C) 2016 Wiley Periodicals, Inc.
引用
收藏
页码:178 / 188
页数:11
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