Same but Different: Dipole-Stabilized Shape Resonances in CuF鈥?/sup> and AgF鈥?/sup>

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• 作者：Thomas-C. Jagau ; Diep B. Dao ; Nicholas S. Holtgrewe ; Anna I. Krylov ; Richard Mabbs
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2015
• 出版时间：July 16, 2015
• 年：2015
• 卷：6
• 期：14
• 页码：2786-2793
• 全文大小：410K
• ISSN：1948-7185

文摘

Electron attachment to closed-shell molecules is a gateway to various important processes in the gas and condensed phases. The properties of an electron-attached state, such as its energy and lifetime as well as the character of the molecular orbital to which the electron is attached, determine the fate of the anion. In this experimental and theoretical study of copper and silver fluoride anions, we introduce a鈥?new type of metastable anionic state. Abrupt changes in photoelectron angular distributions point to the existence of autodetaching states. Equation-of-motion coupled-cluster singles and doubles calculations augmented by a complex absorbing potential identify some of these states as 危 and 螤 dipole-stabilized resonances, a new type of shape resonance. In addition, these molecules support valence and dipole-bound states and a 危 resonance of charge-transfer character. By featuring five different types of anionic states, they provide a vehicle for studying fundamental properties of anions and for validating new theoretical approaches for metastable states.