Roy Ram Kinkar, Usha V, Paulovic Jozef, Hirao Kimihiko
Department of Chemistry, Birla Institute of Technology and Science (BITS), Pilani-333031, Rajasthan, India.
J Phys Chem A. 2005 May 26;109(20):4601-6. doi: 10.1021/jp046505j.
Density functional theory based global and local electrophilicity descriptors are used to study the reliability of local electrophilicity values of the strongest electrophilic sites in generating global intermolecular electrophilicity trends. The evaluated values on 15 different organic chlorides show that, for systems having more than one comparatively strong electrophilic site, the local electrophilicity value of the strongest site does not produce a reliable global intermolecular electrophilicity trend. But for systems having one distinctly strong electrophilic site it does. The analytical explanation in favor of the above observation is also provided. Thus, what was argued in an earlier study (Roy, R. K. J. Phys. Chem. 2004, 108, 4934) is established strongly by numerical demonstrations as well as analytical reasoning in the present one.
基于密度泛函理论的全局和局部亲电性描述符用于研究最强亲电位点的局部亲电性值在生成全局分子间亲电性趋势方面的可靠性。对15种不同有机氯化物的评估值表明，对于具有多个相对较强亲电位点的体系，最强位点的局部亲电性值不会产生可靠的全局分子间亲电性趋势。但对于具有一个明显强亲电位点的体系则会产生。还提供了支持上述观察结果的分析解释。因此，早期研究（罗伊，R.K.《物理化学杂志》2004年，108卷，4934页）中的观点在本研究中通过数值论证以及分析推理得到了有力证实。
