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Small Polarons in Two-Dimensional Pnictogens: A First-Principles Study

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    Physical Insights into Materials and Molecular Properties

    Small Polarons in Two-Dimensional Pnictogens: A First-Principles Study
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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2021, 12, 19, 4674–4680
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    https://doi.org/10.1021/acs.jpclett.1c00929
    Published May 12, 2021
    Copyright © 2021 American Chemical Society
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    Abstract

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    We report the first-principles study of small polarons in the most stable two-dimensional pnictogen allotropes: blue and black phosphorene and arsenene. While both cations and anions of small hydrogen-passivated clusters show charge localization and local lattice distortions, only the hole polaron in the blue allotrope is stable in the infinite size cluster limit. The adiabatic polaron relaxation energy is found to be 0.1 eV for phosphorene and 0.15 eV for arsenene. The polaron is localized on lone-pair orbitals with half of the extra charge distributed among 13 atoms. In the blue phosphorene, these orbitals form the valence band’s top with a relatively flat band dispersion. However, in the black phosphorene, lone-pair orbitals hybridize with bonding orbitals, which explains the difference in hole localization strength between the two topologically equivalent allotropes. The polaron’s adiabatic barriers for motion are small compared to the most strongly coupled phonon frequency, implying the polaron barrierless motion.

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    Supporting Information

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    The following files are available free of charge: The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpclett.1c00929.

    • Tables and figures of considered clusters, size convergence studies of undistorted clusters and hole polaron in blue-P, benchmarking basis sets and density functionals, calculated parameters and electronic structure of monolayers, polaron wave-function and lattice deformation, potential energy surfaces and electron-phonon couplings, excited states, triplet exciton, results for arsenic and antimony, reference atomic data for pnictogens, dependence on cluster passivation (PDF)

    • Atomic coordinates of considered phosphorus monolayers and clusters (listed in Section S1) and natural orbitals of small clusters in Gaussian log-file format readable by Jmol program (Figure S20, Figure 4a, Figure S39) (ZIP)

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    This article is cited by 9 publications.

    1. Hong-Shun He, Yun-Bo Li, Jifeng Luo, Qingxia Ge, Jian Wu, Daifeng Zou, Ying Xu, Wen-Jin Yin. Tunable transport mode of polaron in polarized Janus MoSSe few-layer structures: a constrained density functional theory study. Dalton Transactions 2025, 3 https://doi.org/10.1039/D4DT02909G
    2. Zhizhen Ren, Zhijian Shi, Haifeng Feng, Zhongfei Xu, Weichang Hao. Recent Progresses of Polarons: Fundamentals and Roles in Photocatalysis and Photoelectrocatalysis. Advanced Science 2024, 11 (37) https://doi.org/10.1002/advs.202305139
    3. Vasilii Vasilchenko, Xavier Gonze. Polarons in the cubic generalized Fröhlich model: Spontaneous symmetry breaking. Physical Review B 2024, 109 (18) https://doi.org/10.1103/PhysRevB.109.184301
    4. Vo Van On, J. Guerrero-Sanchez, D. M. Hoat. Modifying the electronic and magnetic properties of the scandium nitride semiconductor monolayer via vacancies and doping. Physical Chemistry Chemical Physics 2024, 26 (4) , 3587-3596. https://doi.org/10.1039/D3CP04977A
    5. Huiru Liu, Aolei Wang, Ping Zhang, Chen Ma, Caiyun Chen, Zijia Liu, Yi-Qi Zhang, Baojie Feng, Peng Cheng, Jin Zhao, Lan Chen, Kehui Wu. Atomic-scale manipulation of single-polaron in a two-dimensional semiconductor. Nature Communications 2023, 14 (1) https://doi.org/10.1038/s41467-023-39361-0
    6. Andriy Zhugayevych, Kun-Han Lin, Denis Andrienko. Electronic coarse-graining of long conjugated molecules: Case study of non-fullerene acceptors. The Journal of Chemical Physics 2023, 159 (2) https://doi.org/10.1063/5.0155488
    7. Ling Zhang, Guo-Xiang Zhi, Qingling Meng, Wenzhen Dou, Chenqiang Hua, Lu Sun, Miao Zhou. Polaronic defects in monolayer CeO2: Quantum confinement effect and strain engineering. The Journal of Chemical Physics 2022, 157 (19) https://doi.org/10.1063/5.0122958
    8. Vasilii Vasilchenko, Andriy Zhugayevych, Xavier Gonze. Variational polaron equations applied to the anisotropic Fröhlich model. Physical Review B 2022, 105 (21) https://doi.org/10.1103/PhysRevB.105.214301
    9. Joao C. de Abreu, Jean Paul Nery, Matteo Giantomassi, Xavier Gonze, Matthieu J. Verstraete. Spectroscopic signatures of nonpolarons: the case of diamond. Physical Chemistry Chemical Physics 2022, 24 (20) , 12580-12591. https://doi.org/10.1039/D2CP01012G
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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2021, 12, 19, 4674–4680
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpclett.1c00929
    Published May 12, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

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