Abstract
Electron transfer and transport constitute the fundamental mechanisms governing the performance of polymeric dielectrics, yet their microscopic nature remains elusive due to the intrinsic complexity of aperiodic condensed states. This investigation presents, for the first time, a computational-experimental exploration on quantitative, real-space orbital electron transfer and quantum electron transport, which have been largely overlooked in aperiodic systems. The energy barrier and spatial confinement of unoccupied frontier orbitals play a pivotal role in regulating electron transfer, which is predictable and experimentally characterizable, and dictates dielectric performance. Additionally, the structure-dependent quantum current strongly influences the macroscopic conduction characteristics. These insights enable precise regulation of dielectric performance via chemically superseding frontier orbitals. We hence apply this approach to a typical polymeric system and propose a design principle comprising three ab-initio descriptors. Our results substantiate the validity of this rationale, offering renewed insights into electron dynamics in aperiodic systems and guiding future dielectric design.
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The data that support the findings of this study are available from the corresponding author upon reasonable request. The underlying code for this study is not publicly available but may be made available to qualified researchers on reasonable request from the corresponding author.
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The underlying code for this study is not publicly available but may be made available to qualified researchers on reasonable request from the corresponding author.
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Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (grant numbers 52507182, 52237001, and 52525303). The first author acknowledges the financial support from the IEEE DEIS Graduate Fellowship, and the technical discussions with Dr. Mingcong Yang, Dr. Shaojie Wang, Dr. Zhen Luo, and Dr. Junluo Li graduated from Tsinghua University.
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S.H. performed all computational investigations, all experimental characterizations except for Nano-ISPD, and completed the writing of this manuscript. L.M. performed the Nano-ISPD characterization. M.W., J.Z., and H.Y. contributed to the synthesis of the materials. J.H., Q.L., and J.L.H. conceived, planned, and supervised the project. All authors have read and approved the manuscript.
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Hu, S., Meng, L., Wang, M. et al. Rational design of polymeric dielectrics guided by insightful understanding of electron transfer/transport in aperiodic systems. npj Comput Mater (2026). https://doi.org/10.1038/s41524-026-02052-7
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DOI: https://doi.org/10.1038/s41524-026-02052-7
