Accurate description of charged excitations in molecular solids from embedded many-body perturbation theory
Accurate description of charged excitations in molecular solids from embedded many-body perturbation theory
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DOI：
10.1103/physrevb.97.035108
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发表时间：
2018-01
影响因子：
3.7
通讯作者：
Jing Li;G. D’Avino;I. Duchemin;D. Beljonne;X. Blase
中科院分区：
文献类型：
--
作者：
Jing Li;G. D’Avino;I. Duchemin;D. Beljonne;X. Blase
基于多体绿色函数GW形式，提出了一种新的量子/经典混合方法来计算分子固体中的带电激发。在GW水平上描述的分子嵌入到用精确的经典极化方案建模的结晶环境中。这允许计算的电子添加和去除能量的散装和在晶体表面的带电激发光电子实验中探测。通过考虑并五苯和全氟并五苯晶体的典型情况，我们讨论了分子间相互作用对电子能级的不同贡献，区分了极化（结合量子和经典极化率）和晶体场效应（可影响高达±0.6 eV的能级）。引入能带色散后，我们实现定量协议（0.2 eV内）的电离势和电子亲合势测量并五苯和perfluoropentacene晶体表面的特征在于站立的分子。
We present a novel hybrid quantum/classical approach to the calculation of charged excitations in molecular solids based on the many-body Green's function GW formalism. Molecules described at the GW level are embedded into the crystalline environment modeled with an accurate classical polarizable scheme. This allows the calculation of electron addition and removal energies in the bulk and at crystal surfaces where charged excitations are probed in photoelectron experiments. By considering the paradigmatic case of pentacene and perfluoropentacene crystals, we discuss the different contributions from intermolecular interactions to electronic energy levels, distinguishing between polarization, which is accounted for combining quantum and classical polarizabilities, and crystal field effects, that can impact energy levels by up to ±0.6 eV. After introducing band dispersion, we achieve quantitative agreement (within 0.2 eV) on the ionization potential and electron affinity measured at pentacene and perfluoropentacene crystal surfaces characterized by standing molecules.