利用代数图解构造理论与极化嵌入模拟真实化学环境中的电离态
Simulating Ionized States in Realistic Chemical Environments With Algebraic Diagrammatic Construction Theory and Polarizable Embedding
AI总结：
本文提出结合极化嵌入的代数图解构造理论方法PE-IP-ADC，用于精确模拟凝聚相环境中电离态，并通过计算水中胸腺嘧啶的垂直电离能验证了其与实验高度吻合的准确性。
摘要：
电子脱离过程的理论模拟对于理解化学氧化还原反应、半导体与电化学性质以及高能辐射损伤至关重要。然而，由于电离电子态具有开壳层特性、电子关联效应的重要性以及与化学环境的强相互作用，对其进行精确计算极具挑战性。在本工作中，我们提出了一种基于代数图解构造理论与极化嵌入的高效方法，能够精确模拟凝聚相或生物化学环境中的电离电子态（PE-IP-ADC）。我们通过计算胸腺嘧啶分子在体相水中溶剂化时的垂直电离能（VIE）展示了PE-IP-ADC的能力。结果表明，二阶和三阶PE-IP-ADC方法结合三ζ质量基组得到的溶剂诱导VIE位移分别为-0.92和-0.93 eV，与实验估计值-0.9 eV高度吻合。本工作证明了PE-IP-ADC方法在模拟真实化学环境中带电电子态方面的能力，并推动了其进一步发展。
英文摘要：
Theoretical simulations of electron detachment processes are vital for understanding chemical redox reactions, semiconductor and electrochemical properties, and high-energy radiation damage. However, accurate calculations of ionized electronic states are very challenging due to their open-shell nature, importance of electron correlation effects, and strong interactions with chemical environment. In this work, we present an efficient approach based on algebraic diagrammatic construction theory with polarizable embedding that allows to accurately simulate ionized electronic states in condensed-phase or biochemical environments (PE-IP-ADC). We showcase the capabilities of PE-IP-ADC by computing the vertical ionization energy (VIE) of thymine molecule solvated in bulk water. Our results show that the second- and third-order PE-IP-ADC methods combined with the basis of set of triple-zeta quality yield a solvent-induced shift in VIE of -0.92 and -0.93 eV, respectively, in an excellent agreement with experimental estimate of -0.9 eV. This work demonstrates the power of PE-IP-ADC approach for simulating charged electronic states in realistic chemical environments and motivates its further development.
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