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Extending Quantum Chemistry of Bound States to Electronic Resonances
Annual Review of Physical Chemistry ( IF 14.7 ) Pub Date : 2017-05-02 00:00:00 , DOI: 10.1146/annurev-physchem-052516-050622
Thomas-C. Jagau 1 , Ksenia B. Bravaya 2 , Anna I. Krylov 3
Affiliation  

Electronic resonances are metastable states with finite lifetime embedded in the ionization or detachment continuum. They are ubiquitous in chemistry, physics, and biology. Resonances play a central role in processes as diverse as DNA radiolysis, plasmonic catalysis, and attosecond spectroscopy. This review describes novel equation-of-motion coupled-cluster (EOM-CC) methods designed to treat resonances and bound states on an equal footing. Built on complex-variable techniques such as complex scaling and complex absorbing potentials that allow resonances to be associated with a single eigenstate of the molecular Hamiltonian rather than several continuum eigenstates, these methods extend electronic-structure tools developed for bound states to electronic resonances. Selected examples emphasize the formal advantages as well as the numerical accuracy of EOM-CC in the treatment of electronic resonances. Connections to experimental observables such as spectra and cross sections, as well as practical aspects of implementing complex-valued approaches, are also discussed.

中文翻译:


将束缚态的量子化学扩展到电子共振

电子共振是亚稳态,在电离或脱离连续体中具有有限的寿命。它们在化学,物理和生物学中无处不在。共振在DNA放射分解,等离子体激元催化和阿秒光谱等各种过程中起着核心作用。这篇综述描述了新颖的运动方程耦合簇(EOM-CC)方法,旨在在同等条件下处理共振和束缚态。这些方法基于复杂的可变技术(例如复杂的缩放比例和复杂的吸收电势),使共振与分子哈密顿量的单个本征态相关,而不是与几个连续本征态相关联,这些方法将为束缚态开发的电子结构工具扩展到电子共振。所选示例强调了EOM-CC在电子共振治疗方面的形式优势以及数值准确性。还讨论了与实验可观察对象(如光谱和横截面)的连接,以及实现复数值方法的实践方面。

更新日期:2017-05-02
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