Natural orbital Fukui function and application in understanding cycloaddition reaction mechanisms.

A new condensed form of the Fukui function, the natural orbital Fukui function (NOFF), is proposed and derived from natural bond orbital occupancy. It is defined as the change in natural bond orbital occupancy upon electronic perturbation (electron addition to, or depletion from, a molecular system). Applying NOFF to a series of cycloaddition reactions (e.g., [4 + 2] and [2 + 1] cycloadditions) illustrates the effectiveness of the concept in interpreting bond breakage and formation mechanisms.