Molecular structures and intramolecular dynamics of pentahalides

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• 作者：A.A. Ischenko ^{aischenko@yasenevo.ru}
• 关键词：Pentahalides ; Fluxional molecules ; Jahn-Teller effect ; Pseudo-Jahn-Teller effect ; gas electron diffraction ; Spectroscopy ; Quantum chemistry ; Intramolecular dynamics ; Structural instability
• 刊名：Journal of Molecular Structure
• 出版年：2017
• 出版时间：15 March 2017
• 年：2017
• 卷：1132
• 期：Complete
• 页码：109-138
• 全文大小：4364 K
• 卷排序：1132

文摘

This paper reviews advances of modern gas electron diffraction (GED) method combined with high-resolution spectroscopy and quantum chemical calculations in studies of the impact of intramolecular dynamics in free molecules of pentahalides. Some recently developed approaches to the electron diffraction data interpretation, based on direct incorporation of the adiabatic potential energy surface parameters to the diffraction intensity are described. In this way, complementary data of different experimental and computational methods can be directly combined for solving problems of the molecular structure and its dynamics. The possibility to evaluate some important parameters of the adiabatic potential energy surface – barriers to pseudorotation and saddle point of intermediate configuration from diffraction intensities in solving the inverse GED problem is demonstrated on several examples. With increasing accuracy of the electron diffraction intensities and the development of the theoretical background of electron scattering and data interpretation, it has become possible to investigate complex nuclear dynamics in fluxional systems by the GED method. Results of other research groups are also included in the discussion.