激发态的电荷转移分析。

Charge-displacement analysis for excited states.

机构信息

Istituto CNR di Scienze e Tecnologie Molecolari, via Elce di Sotto 8, I-06123 Perugia, Italy.

Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Ferrara, via Borsari 46, I-44100 Ferrara, Italy.

出版信息

J Chem Phys. 2014 Feb 7;140(5):054110. doi: 10.1063/1.4863411.

DOI:10.1063/1.4863411

PMID:24511925

Abstract

We extend the Charge-Displacement (CD) analysis, already successfully employed to describe the nature of intermolecular interactions [L. Belpassi et al., J. Am. Chem. Soc. 132, 13046 (2010)] and various types of controversial chemical bonds [L. Belpassi et al., J. Am. Chem. Soc. 130, 1048 (2008); N. Salvi et al., Chem. Eur. J. 16, 7231 (2010)], to study the charge fluxes accompanying electron excitations, and in particular the all-important charge-transfer (CT) phenomena. We demonstrate the usefulness of the new approach through applications to exemplary excitations in a series of molecules, encompassing various typical situations from valence, to Rydberg, to CT excitations. The CD functions defined along various spatial directions provide a detailed and insightful quantitative picture of the electron displacements taking place.

摘要

我们扩展了电荷转移（CD）分析，该分析已经成功地用于描述分子间相互作用的性质[L. Belpassi 等人，J. Am. Chem. Soc. 132, 13046（2010）]和各种有争议的化学键[L. Belpassi 等人，J. Am. Chem. Soc. 130, 1048（2008）；N. Salvi 等人，Chem. Eur. J. 16, 7231（2010）]，以研究伴随电子激发的电荷通量，特别是至关重要的电荷转移（CT）现象。我们通过对一系列分子中示例激发的应用证明了新方法的有用性，涵盖了从价态到 Rydberg 到 CT 激发的各种典型情况。沿着各种空间方向定义的 CD 函数提供了发生的电子位移的详细和有见地的定量描述。