Ab Initio Study of the SN2 Reaction CH3Cl + Cl- → Cl- + CH3Cl in Supercritical Water with the Polarizable Continuum Model
Ab Initio Study of the SN2 Reaction CH3Cl + Cl- → Cl- + CH3Cl in Supercritical Water with the Polarizable Continuum Model
复制标题
用极化连续体模型从头算研究超临界水中 SN2 反应 CH3Cl + Cl- → Cl- + CH3Cl
DOI：
10.1021/jp962358g
复制
发表时间：
1997
影响因子：
2.9
通讯作者：
J. Tomasi
中科院分区：
文献类型：
--
作者：
C. Pomelli;J. Tomasi
我们提出了一些计算的SN 2反应在环境和超临界水进行溶剂化的连续方法，极化连续模型（PCM）。PCM允许我们进行量子力学（QM）从头计算在几乎所有的QM理论的水平，并允许我们处理溶剂分离的溶质在同一基础上作为一个紧密的反应系统。这两个特点在这里都得到了利用。结果表明，标准的PCM版本是能够重现计算机模拟结果在一个良好的精度水平，除了一个特定范围的P-T值的超临界水的特点是一个大的等温压缩性。对于在此P-T范围内的计算，我们提出了一个PCM配方，给出了与模拟结果吻合良好的结果。
We present some calculations for an SN2 reaction in ambient and supercritical water performed with a continuum method for solvation, the polarizable continuum model (PCM). PCM allows us to perform quantum mechanical (QM) ab initio calculations at almost all the levels of the QM theory and allows us to treat solvent-separated solutes on the same footing as a tight reacting system. Both features are here exploited. The results indicate that the standard PCM version is able to reproduce computer simulation results at a good level of accuracy, with the exception of a specific range of P−T values of supercritical water characterized by a large isothermal compressibility. For calculations in this P−T range we present a PCM formulation giving results in good agreement with results from simulations.