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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Combined quantum mechanical and molecular mechanics studies of the electron-transfer reactions involving carbon tetrachloride in solution
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Combined quantum mechanical and molecular mechanics studies of the electron-transfer reactions involving carbon tetrachloride in solution

机译：溶液中涉及四氯化碳的电子转移反应的量子力学和分子力学联合研究

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摘要

The reductive dechlorination of carbon tetrachloride, CCl4, by a concerted electron transfer-bond breaking mechanism was studied using combined high level quantum mechanical and molecular mechanics (QM/MM) approach. The free energy activation barriers for the first electron-transfer step were determined from the dissociation profiles of CCl4 and (CCl4-)-C-center dot Complexes in aqueous phase using hybrid-free energy QM/MM methodologies. Both density functional and coupled cluster perturbative triples (CCSD(T)) versions of QM/MM methods were investigated. The impact of the implicit solvent description based on continuum (COSMO) solvent models was also analyzed. QM/MM calculations at the CCSD(T)/aug-ce-pVDZ/SPCE level of theory predict that the activation barriers vary from 0.7 to 35.2 kcal/mol for -2.32 and 0.93 V reduction potentials respectively. Good agreement with experimental data for oxide-free iron electrodes (-0.6 to -1.2 V reduction potentials) is observed indicating that the measured activation barriers are consistent with the concerted electron transfer-bond-breaking mechanism.
机译：采用高水平量子力学和分子力学（QM / MM）相结合的方法，研究了通过协同的电子转移键断裂机理对四氯化碳CCl4进行的还原脱氯。使用混合自由能QM / MM方法从CCl4和（CCl4-）-C-中心点复合物在水相中的解离曲线确定了第一步电子转移步骤的自由能活化能垒。研究了QM / MM方法的密度泛函和耦合簇摄动三重（CCSD（T））版本。还分析了基于连续介质（COSMO）溶剂模型的隐式溶剂描述的影响。在CCSD（T）/ aug-ce-pVDZ / SPCE理论水平上进行的QM / MM计算预测，对于-2.32和0.93 V的还原电位，激活势垒分别从0.7到35.2 kcal / mol。观察到与无氧化物铁电极（-0.6至-1.2 V还原电位）的实验数据吻合良好，表明所测得的激活势垒与协同的电子转移键断裂机理一致。

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