用CCSD（T）计算GW近似对低聚并苯的荷电激发
Evaluating the GW Approximation with CCSD(T) for Charged Excitations Across the Oligoacenes
摘要：
带电激发的oligoacene家族的分子，相关的天体物理学和技术应用，被广泛研究，因此提供了一个很好的系统基准的理论方法。在这项工作中，我们评估的性能多体微扰理论的GW近似相对于新的高质量CCSD（T）的参考数据带电激发的并苯。我们比较GW计算与一些混合密度泛函理论的出发点和本征值自洽。特别的重点是阐明GW预测的激发与分子长度增加的趋势，从苯到并六苯。我们发现，GW计算的基础上的最佳调谐范围分离的混合（OTRSH）的密度泛函和本征值自洽的起点可以产生定量电离势的并苯。然而，对于较大的并苯，预测的电子亲合势可以偏离参考值相当大。我们的工作铺平了道路，预测和具有成本效益的GW计算的带电激发的分子，并确定了某些限制，目前的GW方法在实践中使用的较大的分子。
英文摘要：
Charged excitations of the oligoacene family of molecules, relevant for astrophysics and technological applications, are widely studied and therefore provide an excellent system for benchmarking theoretical methods. In this work, we evaluate the performance of many-body perturbation theory within the GW approximation relative to new high-quality CCSD(T) reference data for charged excitations of the acenes. We compare GW calculations with a number of hybrid density functional theory starting points and with eigenvalue self-consistency. Special focus is given to elucidating the trend of GW-predicted excitations with molecule length increasing from benzene to hexacene. We find that GW calculations with starting points based on an optimally tuned range-separated hybrid (OTRSH) density functional and eigenvalue self-consistency can yield quantitative ionization potentials for the acenes. However, for larger acenes, the predicted electron affinities can deviate considerably from reference values. Our work paves the way for predictive and cost-effective GW calculations of charged excitations of molecules and identifies certain limitations of current GW methods used in practice for larger molecules.
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