Structural, Energetic, and Electronic Properties of La(III)鈥揇imethyl Sulfoxide Clusters
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- 作者：Enrico Bodo ; Mara Chiricotto ; Riccardo Spezia
- 刊名：Journal of Physical Chemistry A
- 出版年：2014
- 出版时间：December 11, 2014
- 年：2014
- 卷：118
- 期：49
- 页码：11602-11611
- 全文大小：531K
- ISSN：1520-5215
文摘
By using accurate density functional theory calculations, we have studied the cluster complexes of a La3+ ion interacting with a small number of dimethyl sulfoxide (DMSO) molecules of growing size (from 1 to 12). Extended structural, energetic, and electronic structure analyses have been performed to provide a complete picture of the physical properties that are the basis of the interaction of La(III) with DMSO. Recent experimental data in the solid and liquid phase have suggested a coordination number of 8 DMSO molecules with a square antiprism geometry arranged similarly in the liquid and crystalline phases. By using a cluster approach on the La3+(DMSO)n gas phase isolated structures, we have found that the 8-fold geometry, albeit less regular than in the crystal, is probably the most stable cluster. Furthermore, we provide new evidence of a 9-fold complexation geometric arrangement that is competitive (at least energetically) with the 8-fold one and that might suggest the existence of transient structures with higher coordination numbers in the liquid phase.