极化连续介质模型与格林函数GW形式：溶剂电子的动力学
Polarizable Continuum Models and Green's Function $\bf{GW}$ Formalism: On the Dynamics of the Solvent Electrons
AI总结：
本文研究极化连续介质模型中溶剂电子动力学对GW计算的影响，证明用ε∞光学介电常数近似频率依赖性仅引入百分之几的误差，并提出单极点模型实现完全动态嵌入GW计算。
摘要：
用于计算电离势或电子亲和势的多体GW形式依赖于由电子自由度构建的频率相关介电函数。考虑在水作为溶剂并在极化连续介质模型中处理的情形，我们探索了将溶剂电子介电响应的完整频率依赖性限制为频率无关的(ε∞)光学介电常数所产生的影响。对于呈现从小到大最高占据分子轨道到最低未占据分子轨道能隙的溶质，我们表明这种限制对从气相到溶剂化相的能级移动所引入的误差不超过百分之几。我们进一步引入了一个非常精确的单极点模型，用于模拟可见光-紫外范围内水的介电函数完整频率依赖性的效应。这使得仅需知道针对ε∞光学介电常数计算的空腔反应场，即可进行完全动态嵌入的GW计算。
英文摘要：
The many-body $GW$ formalism, for the calculation of ionization potentials or electronic affinities, relies on the frequency-dependent dielectric function built from the electronic degrees of freedom. Considering the case of water as a solvent treated within the polarizable continuum model, we explore the impact of restricting the full frequency-dependence of the solvent electronic dielectric response to a frequency-independent $(ε_\infty)$ optical dielectric constant. For solutes presenting small to large highest-occupied to lowest-unoccupied molecular orbital energy gaps, we show that such a restriction induces errors no larger than a few percent on the energy level shifts from the gas to the solvated phase. We further introduce a remarkably accurate single-pole model for mimicking the effect of the full frequency dependence of the water dielectric function in the visible-UV range. This allows a fully dynamical embedded $GW$ calculation with the only knowledge of the cavity reaction field calculated for the $ε_\infty$ optical dielectric constant.
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