Asymmetric rotations slow down diffusion under confinement

Abstract Translation and rotation are the two most fundamental forms of diffusion, yet their coupling mechanism is not clear, especially under confinement. Here, we provided evidence of the coupling between rotation and translation using a substituted benzene molecule as an example. A counterintuiti...

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Main Authors: Zhiqiang Liu, Xun Kan, Mingbin Gao, Yi Ji, Fangxiu Ye, Jingyi Tan, Fengqing Liu, Jiamin Yuan, Xiaomin Tang, Haohan Li, Pan Gao, Jiaao Xue, Qun Cai, Naresh C. Osti, Niina H. Jalarvo, Cheng Li, Yongcun Zou, Yi Li, Shutao Xu, Guangjin Hou, Mao Ye, Fujian Liu, Anmin Zheng
Format: Article
Language:English
Published: Nature Portfolio 2025-02-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-57242-6
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Summary:Abstract Translation and rotation are the two most fundamental forms of diffusion, yet their coupling mechanism is not clear, especially under confinement. Here, we provided evidence of the coupling between rotation and translation using a substituted benzene molecule as an example. A counterintuitive behavior was observed where the movement of the smaller molecule with an asymmetric shape was unexpectedly slower than the larger one with a symmetric shape in confined channels of zeolite. We showed that this diffusion behavior was caused by the presence of the specific and selective interaction of the asymmetric guest with the pores, which increased the local restricted residence time, thus inhibiting the translation under confinement, as further confirmed by dynamic breakthrough curves, uptake measurements, quasi-elastic neutron scattering, and 2H solid-state NMR techniques. Our work correlated asymmetric rotation and diffusion under a confined environment, which enriched our understanding of the coupling between rotation and translation and could shed light on a fundamental understanding of the diffusion process.
ISSN:2041-1723