958-964In this work we explore new insights arising
from simple indices intended to measure the average local vertical ionization
energy associated to ELF valence population basins. The model has been
computationally tested on simple isothiocyanate compounds (R-N=C=S) revealing
that the proposed relationships correctly establish both the inductive and
electronegativity effects of electronegative groups along the examined series,
i.e., methyl- < germyl- < hydrogen- < acetyl-
< chlorodifluoroacetyl-, in agreement with the available experimental
observations. The proposed energetical descriptors are expected to contribute
to the search of relationships between the spatial topology of electronic
populations and energetical aspects of the bonding. The present results enhance
the possibility of gaining insight into chemical bonding and reactivity within
the ELF topological-defined framework of chemical rationalization