Understanding the intrinsic Li–H
2 interaction, decoupled from substrate effects, is essential to rationalize the performance of lithium-decorated hydrogen storage materials. To address the current lack of a clean theoretical baseline, we characterized the sequential H
2 adsorption on the gas-phase Li
6
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Understanding the intrinsic Li–H
2 interaction, decoupled from substrate effects, is essential to rationalize the performance of lithium-decorated hydrogen storage materials. To address the current lack of a clean theoretical baseline, we characterized the sequential H
2 adsorption on the gas-phase Li
6 superatomic cluster using high-level density functional theory (DFT), complemented by Energy Decomposition Analysis (EDA), QTAIM, and NICS(0) calculations. Li
6 acts as a structurally rigid platform (RMSD < 0.032 Å) where ligand-induced polarization progressively strengthens its σ-aromaticity (NICS(0) from −2.917 to −13.98 ppm) and increases the HOMO–LUMO gap up to 5.05 eV. EDA identifies the binding as field-activated physisorption, electrostatically dominated (65–67%) and mechanistically distinct from Kubas coordination, as confirmed by QTAIM closed-shell interaction parameters. Negative cooperativity governs an effective loading capacity of
n = 2 molecules under cryogenic conditions (T
eq = 143.76 and 114.64 K), while an entropic bottleneck renders higher loading non-spontaneous at all temperatures. These results establish Li
6(H
2)
n as a foundational gas-phase reference, providing a systematic, contamination-free descriptor set for the intrinsic Li–H
2 interaction. This framework is essential for isolating the electronic role of the lithium superatom and unambiguously identifying substrate-induced modulations in supported hydrogen storage materials.
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