Structures, Vibrational Frequencies, and Stabilities of Halogen Cluster Anions and Cations, Xn+/鈥?/sup>, n = 3, 4, and 5
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- 作者：K. Sahan Thanthiriwatte ; Jason M. Spruell ; David A. Dixon ; Karl O. Christe ; H. Donald B. Jenkins
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：August 4, 2014
- 年：2014
- 卷：53
- 期：15
- 页码：8136-8146
- 全文大小：471K
- ISSN：1520-510X
文摘
The structures, vibrational frequencies, and thermodynamic stabilities of the homonuclear polyhalogen ions, Xb>3 b>+, Xb>3 b>鈥?/sup>, Xb>4 b>+, Xb>4 b>鈥?/sup>, Xb>5 b>+, and Xb>5 b>鈥?/sup> (X = Cl, Br, I), have been calculated at the CCSD(T) level. The energetics were calculated using the Feller鈥揚eterson鈥揇ixon approach for the prediction of reliable enthalpies of formation. The calculations allow the following predictions where stabilities are defined in terms of thermodynamic quantities. (1) The Xb>3 b>+ cations are stable toward loss of Xb>2 b>; (2) the Xb>3 b>鈥?/sup> anions are marginally stable toward loss of Xb>2 b> with Clb>3 b>鈥?/sup> being the least stable; (3) the Xb>4 b>+ cations and Xb>4 b>鈥?/sup> anions are only weakly bound dimers of Xb>2 b>+1/2 and Xb>2 b>鈥?/2 units, respectively, but the cations are marginally stable toward decomposition to Xb>3 b>+ and X, with Ib>4 b>+ having the lowest dissociation energy, whereas the Xb>4 b>鈥?/sup> anions decompose spontaneously to Xb>3 b>鈥?/sup> and X; (4) the Xb>5 b>+ cations are only marginally stable at low temperatures toward loss of Xb>2 b>, with Clb>5 b>+ being the least stable; and (5) the Xb>5 b>鈥?/sup> anions are also only stable at low temperatures toward loss of Xb>2 b>, with Clb>5 b>鈥?/sup> being the least stable.