Variation in electrophilicity on electronic excitation

Abstract

AbstractThe rationality of the minimum electrophilicity principle (MElP) as a companion of minimum polarizability principle and maximum hardness principle is studied for simple diatomic, triatomic, and tetratomic molecules. The applicability is further justified considering organic molecules (e.g., pyrene and acridine yellow) are known for their photophysical properties and accordingly their excited state properties. Single excitation CI (CIS) and time‐dependent density functional theory (TDDFT) are employed to study the excited state reactivity. Two types of excitations, namely vertical and adiabatic, are considered. Processes involving conservation and change in spin multiplicity are included during excitation. The general trend is that the molecules are less electrophilic in the ground state than those in the corresponding excited states. It is found that adiabatic excitation validates the principle even for the triplet ground state molecules undergoing an excitation where spin multiplicity gets altered. The TDDFT method explains the validity of the MElP augmenting the CIS method. This study echoed the MElP during molecular electronic excitation.