In this work, the Coulson‐Longuet‐Higgins response function (atom‐atomic polarizabilities [AAPs]) is used to describe the transfer of an electron perturbation in π‐conjugated systems in the presence of a static electric field. Computations are performed using different many‐electron approaches to study the effect. An accurate account of the electron correlation is shown to play a key role in the description of the interaction of a π‐shell with the external electrostatic field. Studies in this work reveal that the Hückel theory widely used in calculations of electron‐perturbation transfer is not reliable even at the qualitative level to describe the effects studies in this work. However, the π‐electron coupled cluster theory has been proven capable of providing a reliable electronic structure (among them, AAPs and excitation energies) that agree with the results obtained with the π‐electron full configuration‐interaction approach. The calculations also show that these properties have an essentially nonlinear character in terms of the strength of the applied electric field. The results obtained in the present work can provide useful information relevant to the application of π‐conjugated systems in molecular electronics.

中文翻译：

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π共轭体系在电场存在下的电子摄动效应：电子相关性研究

在这项工作中，Coulson-Longuet-Higgins响应函数（原子-原子极化率[AAP]）用于描述在存在静电电场的情况下，π共轭体系中电子扰动的转移。使用不同的多电子方法进行计算以研究其影响。在描述π壳与外部静电场之间的相互作用时，显示出对电子相关性的准确描述至关重要。这项工作的研究表明，在电子微扰传递计算中广泛使用的Hückel理论即使在定性水平上也不能可靠地描述这项工作的影响研究。但是，π电子耦合簇理论已被证明能够提供可靠的电子结构（其中，AAP和激发能）与π电子全组态相互作用方法获得的结果一致。计算还表明，就所施加的电场强度而言，这些性质具有基本上非线性的特性。在本工作中获得的结果可以提供与π共轭体系在分子电子学中的应用有关的有用信息。