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

Huziel Saucceda
Stefan Chmiela
Valentin Vassilev Galindo
Alexandre Tkatchenko
Nature Communications, vol. 12 (2021), pp. 442


Nuclear quantum effects (NQE) tend to generate delocalized molecular dynamics due to the anharmonicity of interatomic interactions. Here, we present evidence that NQE often enhance electronic interactions and, in turn, can result in dynamical molecular stabilization at finite temperature. The underlying physical mechanism promoted by NQE depends on the particular interaction under consideration. First, the effective reduction of interatomic distances between functional groups within a molecule enhances the n → π ∗ interaction by increasing the overlap between molecular orbitals or by strengthening electrostatic interactions between neighboring charge densities. Second, NQE can localize methyl rotors by temporarily changing molecular bond orders and leading to the emergence of localized transient rotor states. Third, for noncovalent interactions the strengthening comes from the increase of the polarizability given the expanded average interatomic distances induced by NQE. The implications of these boosted interactions include counterintuitive hydroxyl–hydroxyl bonding, hindered methyl rotor dynamics, and molecular stiffening which generates smoother free-energy surfaces. These results challenge the general assumption that NQE tend to mainly generate delocalized dynamics and reveal that NQE also play an active role in dynamical strengthening of molecular interactions. Our findings yield new insights into the versatile role of nuclear quantum fluctuations in molecules and materials

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