标题： 非晶聚合物光电子能谱中的峰展宽：静电景观的主导作用 显示英文标题

标题： Peak Broadening in Photoelectron Spectroscopy of Amorphous Polymers: the Leading Role of the Electrostatic Landscape

摘要： 聚合物光电子能谱的展宽可以归因于几个因素，如光源展宽、光谱仪分辨率、空穴态的有限寿命以及固态效应。 在这里，我们首次建立了一个计算协议，通过使用密度泛函理论、多体微扰理论和经典极化嵌入的组合，评估了四种无定形聚合物在固态效应对芯能级和价能级的影响下引起的峰展宽。 我们表明，静电环境中内在的局部不均匀性在芯能级和半价电子的结合能中诱导了$0.2$-$0.7$~eV 的高斯展宽，对应于所研究系统的半高全宽（FWHM）为$0.5$-$1.7$~eV。 诱导的展宽在丙烯酸酯基聚合物中比在苯乙烯基聚合物中更大，揭示了极性基团在控制固态矩阵中静电地形粗糙度的关键作用。 显示英文摘要

摘要： The broadening in photoelectron spectra of polymers can be attributed to several factors, such as light source spread, spectrometer resolution, finite lifetime of the hole state, and solid-state effects. Here, for the first time, we set up a computational protocol to assess the peak broadening induced for both core and valence levels by solid-state effects in four amorphous polymers by using a combination of density functional theory, many-body perturbation theory, and classical polarizable embedding. We show that intrinsic local inhomogeneities in the electrostatic environment induce a Gaussian broadening of $0.2$-$0.7$~eV in the binding energies of both core and semi-valence electrons, corresponding to a full width at half maximum (FWHM) of $0.5$-$1.7$~eV for the investigated systems. The induced broadening is larger in acrylate- than in styrene- based polymers, revealing the crucial role of polar groups in controlling the roughness of the electrostatic landscape in the solid matrix.