Nature of proton transport in a water-filled carbon nanotube and in liquid water

Literature Information

Publication Date 2013-03-07
DOI 10.1039/C3CP50218J
Impact Factor 3.676
Authors

Ji Chen, Qianfan Zhang, Angelos Michaelides, Enge Wang


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Abstract

Proton transport (PT) in bulk liquid water and within a thin water-filled carbon nanotube has been examined using ab initio path-integral molecular dynamics (PIMD). Barrierless proton transfer is observed in each case when quantum nuclear effects (QNEs) are accounted for. The key difference between the two systems is that in the nanotube facile PT is facilitated by a favorable pre-alignment of water molecules, whereas in bulk liquid water solvent reorganization is required prior to PT. Configurations where the quantum excess proton is delocalized over several adjacent water molecules along with continuous interconversion between different hydration states reveals that, as in liquid water, the hydrated proton under confinement is best described as a fluxional defect, rather than any individual idealized hydration state such as Zundel, Eigen, or the so-called linear H7O3+ complex along the water chain. These findings highlight the importance of QNEs in intermediate strength hydrogen bonds (HBs) and explain why H+ diffusion through nanochannels is impeded much less than other cations.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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