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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Solvent Effects on the Vibrational Frequencies of the Phenolate Anion,the para-Cresolate Anion,and Their Radicals
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Solvent Effects on the Vibrational Frequencies of the Phenolate Anion,the para-Cresolate Anion,and Their Radicals

机译：溶剂对酚酸酯，对甲酚酸酯及其自由基的振动频率的影响

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摘要

The effects of aqueous solvation on the structure and vibrational frequencies of phenol,para-cresol,and their respective radicals are calculated at the B3LYP/6-31+G(d,p)level of theory using the conductor-like polarizable continuum model(C-PCM)alone and in combination with an explicit water molecule H-bonded to the phenolic oxygen.Calculated vibrational frequencies are compared to experimental frequencies obtained in aqueous buffer at high pH.For all models,the C-PCM provides the best overall agreement between theory and experiment at a modest computational effort,as demonstrated by the lowest mean absolute deviations in the computed frequencies.In addition,the C-PCM provides anion Wilson mode 7a ~(18)O isotope shifts in excellent agreement with experiment and improves agreement between the computed and observed radical Wilson mode 7a ~2H isotope shift.On the basis of a quantitative comparison of the anion and radical normal modes by vibrational projection analysis and total energy decomposition,an alternative criterion for distinguishing the anion and radical Wilson modes 7a and 19a using the relative phasing of the carbon-oxygen and carbon-carbon bond stretches is presented.
机译：在B3LYP / 6-31 + G（d，p）的理论水平下，使用类似于导体的可极化连续体模型，计算了水溶剂化对苯酚，对甲酚及其各自自由基的结构和振动频率的影响（ C-PCM）单独使用，并与H键合在酚氧上的显式水分子结合使用。将计算出的振动频率与在高pH条件下在水性缓冲液中获得的实验频率进行比较。对于所有型号，C-PCM提供了最佳的总体一致性C-PCM提供阴离子威尔逊模式7a〜（18）O同位素位移，与实验极佳的一致性，并改善了一致性。计算的和观测到的自由基Wilson模式7a〜2H同位素位移之间的关系。在通过振动投影分析和总能量dec定量比较阴离子和自由基正态模的基础上结合，提出了使用碳-氧和碳-碳键段的相对定相区分阴离子和自由基威尔逊模式7a和19a的替代标准。

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