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Asymmetric response of interfacial water to applied electric fields

Author

Listed:
  • Angelo Montenegro

    (University of Southern California)

  • Chayan Dutta

    (University of Southern California)

  • Muhammet Mammetkuliev

    (University of Southern California)

  • Haotian Shi

    (University of Southern California)

  • Bingya Hou

    (University of Southern California)

  • Dhritiman Bhattacharyya

    (University of Southern California)

  • Bofan Zhao

    (University of Southern California)

  • Stephen B. Cronin

    (University of Southern California)

  • Alexander V. Benderskii

    (University of Southern California)

Abstract

Our understanding of the dielectric response of interfacial water, which underlies the solvation properties and reaction rates at aqueous interfaces, relies on the linear response approximation: an external electric field induces a linearly proportional polarization. This implies antisymmetry with respect to the sign of the field. Atomistic simulations have suggested, however, that the polarization of interfacial water may deviate considerably from the linear response. Here we present an experimental study addressing this issue. We measured vibrational sum-frequency generation spectra of heavy water (D2O) near a monolayer graphene electrode, to study its response to an external electric field under controlled electrochemical conditions. The spectra of the OD stretch show a pronounced asymmetry for positive versus negative electrode charge. At negative charge below 5 × 1012 electrons per square centimetre, a peak of the non-hydrogen-bonded OD groups pointing towards the graphene surface is observed at a frequency of 2,700 per centimetre. At neutral or positive electrode potentials, this ‘free-OD’ peak disappears abruptly, and the spectra display broad peaks of hydrogen-bonded OD species (at 2,300–2,650 per centimetre). Miller’s rule1 connects the vibrational sum-frequency generation response to the dielectric constant. The observed deviation from the linear response for electric fields of about ±3 × 108 volts per metre calls into question the validity of treating interfacial water as a simple dielectric medium.

Suggested Citation

  • Angelo Montenegro & Chayan Dutta & Muhammet Mammetkuliev & Haotian Shi & Bingya Hou & Dhritiman Bhattacharyya & Bofan Zhao & Stephen B. Cronin & Alexander V. Benderskii, 2021. "Asymmetric response of interfacial water to applied electric fields," Nature, Nature, vol. 594(7861), pages 62-65, June.
  • Handle: RePEc:nat:nature:v:594:y:2021:i:7861:d:10.1038_s41586-021-03504-4
    DOI: 10.1038/s41586-021-03504-4
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    Cited by:

    1. Kaian Sun & Xueyan Wu & Zewen Zhuang & Leyu Liu & Jinjie Fang & Lingyou Zeng & Junguo Ma & Shoujie Liu & Jiazhan Li & Ruoyun Dai & Xin Tan & Ke Yu & Di Liu & Weng-Chon Cheong & Aijian Huang & Yunqi Li, 2022. "Interfacial water engineering boosts neutral water reduction," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    2. Yang, Huayu & Yan, Bowen & Chen, Wei & Fan, Daming, 2023. "Prediction and innovation of sustainable continuous flow microwave processing based on numerical simulations: A systematic review," Renewable and Sustainable Energy Reviews, Elsevier, vol. 175(C).
    3. J. Cai & E. Griffin & V. H. Guarochico-Moreira & D. Barry & B. Xin & M. Yagmurcukardes & S. Zhang & A. K. Geim & F. M. Peeters & M. Lozada-Hidalgo, 2022. "Wien effect in interfacial water dissociation through proton-permeable graphene electrodes," Nature Communications, Nature, vol. 13(1), pages 1-7, December.
    4. Chao-Yu Li & Ming Chen & Shuai Liu & Xinyao Lu & Jinhui Meng & Jiawei Yan & Héctor D. Abruña & Guang Feng & Tianquan Lian, 2022. "Unconventional interfacial water structure of highly concentrated aqueous electrolytes at negative electrode polarizations," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
    5. Kit Joll & Philipp Schienbein & Kevin M. Rosso & Jochen Blumberger, 2024. "Machine learning the electric field response of condensed phase systems using perturbed neural network potentials," Nature Communications, Nature, vol. 15(1), pages 1-12, December.

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