Unravelling the influence of quantum proton delocalization on electronic charge transfer through the hydrogen bond

Abstract

Upon hydrogen bond formation, electronic charge density is transferred between the donor and acceptor, impacting processes ranging from hydration to spectroscopy. Here we use ab initio path integral simulations to elucidate the role of nuclear quantum effects in determining the charge transfer in a range of hydrogen bonded species in the gas and liquid phase. We show that the quantization of the nuclei gives rise to large changes in the magnitude of the charge transfer as well as its temperature dependence. We then explain how a single geometric parameter determines the charge transfer through the hydrogen bond. These results thus demonstrate that nuclear quantum effects are vital for the accurate description of charge transfer and offer a physically transparent way to understand how hydrogen bonding gives rise to it.

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Cited by in corpus (4)

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• Charge Transfer as a Ubiquitous Mechanism in Determining the Negative Charge at Hydrophobic Interfaces
• Decisive role of nuclear quantum effects on surface mediated water dissociation at finite temperature
• Quantum Nature of the Hydrogen Bond from Ambient Conditions down to Ultra-low Temperatures