The heterolytic cleavage of H2 by multiply bonded phosphorus-bridged G13-P-P-Rea (G13 = B, Al, Ga, In, and Tl) and G15-P-Ga-Rea (G15 = N, P, As, Sb, and Bi) frustrated Lewis pairs (FLPs) has been theoretically investigated using density functional theory calculations. For the above nine FLP-type molecules, our theoretical findings suggest that only Al-P-P-Rea, Ga-P-P-Rea, and In-P-P-Rea can undergo the energetically feasible H2 activation reaction from kinetic and thermodynamic viewpoints. Our study based on the activation strain model (ASM) reveals that gaining a better orbital overlap between G13-P-P-Rea and G15-P-Ga-Rea molecules and H2 affected the reaction barriers through the atomic radius of G13 and G15. According to our energy decomposition analysis-natural orbitals for chemical valence (EDA-NOCV) results, the bonding of these H2 activation reactions involving G13-P-P-Rea and G15-P-Ga-Rea is dominated by the donor-acceptor interaction (singlet-singlet interaction) rather than the electron-sharing interaction (triplet-triplet interaction). Moreover, our EDA-NOCV evidence reveals that the best description for the above bonding situations is the lone pair(G15) → σ*(H2) interaction rather than the empty p-π-orbital(G13) ← σ(H2) interaction. In particular, the findings in this work based on theoretically calculated geometries and the corresponding relative free energies of the stationary points combined with the results from the above sophisticated methods nicely agree with the famous Hammond postulate.