To rationalize this negative pKa correlation with E(Li-N 2 ) we consider the fundamental chemistry underlying the lithium-catalyzed nitrogen reduction reaction. To facilitate lithiummediated reduction of nitrogen via its dissociation through nitride formation, lithium must act as a reducing agent to convert nitrogen into its nitride by donating electrons to it (see Eq. 2). While the nitrogen molecule is in itself very stable owing to its triple bond, a strong enough Lewis acid can engage in an electrophilic attack on the nitrogen molecule's terminal lone pairs to make its atoms electron deficient enough to allow the electron transfer from the lithium slab. This is similar to acid-catalyzed hydrolysis of nitriles (R-C≡N:) to carboxylic acids or the reaction of nitriles with organolithium, organo-magnesium or organo-aluminum reagents to form aldehydes. Along these lines, a stronger acid would naturally result in a weaker interaction with the lithium slab by attempting to pull more electrons away from the nitrogen atoms. In support of this rationale, we find that across all calculations, Bader analysis showed a positive charge gain on the lithium slab mostly accompanied by a negative charge gain on the PD, with the notable exceptions being molecules like propane and ethane that are poor electrophiles and have the highest pKa (Table ).