Are the local electrophilicity descriptors reliable indicators of global electrophilicity trends?

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.