On the Stability, Electronic Structure, and Nonlinear Optical Properties of HXeOXeF and FXeOXeF

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• 作者：Aggelos Avramopoulos ; Jiabo Li ; Nicole Holzmann ; Gernot Frenking ; Manthos G. Papadopoulos
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：September 15, 2011
• 年：2011
• 卷：115
• 期：36
• 页码：10226-10236
• 全文大小：1082K
• 年卷期：v.115,no.36(September 15, 2011)
• ISSN：1520-5215

文摘

The electronic ground state, stability, and linear and nonlinear optical properties of HXeOXeF and FXeOXeF have been studied theoretically by employing complete active space valence bond (CASVB), multistate complete active space perturbation theory (MS-CASPT2), and coupled cluster methods. It is shown that the oxygen inserted between the two Xe atoms significantly modifies the ground-state electronic configuration of the formed derivative by increasing the closed-shell contribution (蟽²) and removing the diradicaloid character observed in HXe₂F. The electronic charge distribution has been analyzed by employing the atoms-in-molecules (AIM) method. The dissociation channels of HXeOXeF and FXeOXeF have been studied in detail. It was found that these compounds are metastable, protected by substantial energy barriers and, thus, they can be prepared under appropriate conditions. Both two- and three-body dissociation reactions have been considered. The effects of inserting O in HXe₂F and substituting H (HXeOXeF) by F, leading to FXeOXeF, on the energy barriers are discussed. The significant effects of the inserted oxygen on the polarizability and even more on the first hyperpolarizability have been computed and rationalized.