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Nuclear quantum effects (NQE) tend to generate delocalized molecular dynamicsdue to the inclusion of the zero point energy and its coupling with theanharmonicities in interatomic interactions. Here, we present evidence that NQEoften enhance electronic interactions and, in turn, can result in dynamicalmolecular stabilization at finite temperature. The underlying physicalmechanism promoted by NQE depends on the particular interaction underconsideration. First, the effective reduction of interatomic distances betweenfunctional groups within a molecule can enhance the $n\to\pi^*$ interaction byincreasing the overlap between molecular orbitals or by strengtheningelectrostatic interactions between neighboring charge densities. Second, NQEcan localize methyl rotors by temporarily changing molecular bond orders andleading to the emergence of localized transient rotor states. Third, fornoncovalent van der Waals interactions the strengthening comes from theincrease of the polarizability given the expanded average interatomic distancesinduced by NQE. The implications of these boosted interactions includecounterintuitive hydroxyl--hydroxyl bonding, hindered methyl rotor dynamics,and molecular stiffening which generates smoother free-energy surfaces. Ourfindings yield new insights into the versatile role of nuclear quantumfluctuations in molecules and materials.

Dynamical Strengthening of Covalent and Non-Covalent Molecular Interactions by Nuclear Quantum Effects at Finite Temperature