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