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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Quantum chemical calculations of reduction potentials of AnO(2)(2+)/AnO(2)(+) (An = U, Np, Pu, Am) and Fe3+/Fe2+ couples
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Quantum chemical calculations of reduction potentials of AnO(2)(2+)/AnO(2)(+) (An = U, Np, Pu, Am) and Fe3+/Fe2+ couples

机译：AnO（2）（2 +）/ AnO（2）（+）（An = U，Np，Pu，Am）和Fe3 + / Fe2 +对还原电位的量子化学计算

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摘要

The reduction potentials of the AnO(2)(H2O)(5)(2+)/AnO(2)(H2O)(5)(+) couple (An) U, Np, Pu, and Am) and Fe( (H2O)(6)(3+) to Fe(H2O)(6)(2+) in aqueous solution were calculated at MP2, CASPT2, and CCSD( T) levels of theory. Spin-orbit effects for all species were estimated at the CASSCF level. Solvation of the hydrated metal cations was modeled both by polarizable conductor model (PCM) calculation and by solvating the solutes with over one thousand TIP3P water molecules in the QM/MM framework. The redox reaction energy calculated by QM/MM method agreed well with the PCM method after corrections using the classical Born formula for the contribution from the rest of the solvation sphere and correction for dynamic response of solvent polarization in the MM region. Calculated reduction potentials inclusive of spin-orbit effect, zero-point energy, thermal corrections, entropy effect, and PCM solvation energy were found to be comparable with experimental data. The difference between CASPT2 calculated and experimental reduction energies were less than 35 kJ/mol in all cases, which ensures that CASPT2 ( and CCSD( T)) calculations provide reasonable estimates of the thermochemistry of these reactions.
机译：AnO（2）（H2O）（5）（2 +）/ AnO（2）（H2O）（5）（+）对（An）U，Np，Pu和Am）和Fe（（以MP2，CASPT2和CCSD（T）的理论水平计算水溶液中的H2O）（6）（3+）至Fe（H2O）（6）（2+），估计所有物种的自旋轨道效应为通过极化导体模型（PCM）计算和通过在QM / MM框架中用上千种TIP3P水分子溶解溶质，对水合金属阳离子的溶剂化进行建模，并通过QM / MM方法计算氧化还原反应能。计算后的还原电位包括自旋轨道效应，零点能量在内，使用经典的Born公式校正了其余溶剂化球的贡献并校正了MM区中溶剂极化的动态响应，从而与PCM方法非常吻合。 ，热校正，熵效应和PCM溶剂化能与实验数据相当，CASPT2 cal之间的差异在所有情况下，计算得出的还原能和实验还原能均小于35 kJ / mol，这确保了CASPT2（和CCSD（T））的计算可以合理估算这些反应的热化学性质。

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