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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >F_4~+: A Stable Three-Electron Bonded Complex and a Challenge for Standard ab Initio Computational Methods
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F_4~+: A Stable Three-Electron Bonded Complex and a Challenge for Standard ab Initio Computational Methods

机译：F_4〜+：稳定的三电子键复合物和标准的从头算方法的挑战

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摘要

Qualitative considerations based on a simple molecular-orbital model point to the prediction that the radical cation complex F_4~+ should be stable, with a significant bonding energy, relative to dissociation to the F_2 and F_2~+ fragments. A rectangular minimum is indeed characterized at the ab initio MP2 level, as well as a linear conformer displaying nearly free rotation about the central F-F bond. The Moller-Plesset results are, however, shown to be inconsistent and very poorly converged as the order of perturbation is increased, and to be subject to very strong spin contamination with additional problems of local symmetry breaking in the linear conformer. Higher level calculations of the quadratic configuration interaction or coupled-cluster type, with inclusion of single and double excitations and perturbative treatment of triples (QCISD(T) and CCSD(T)), are performed in their spin-unrestricted and spin-restricted forms. All high-level calculations yield optimized geometries and bonding energies which are consistent with each other and point to the firm conclusion that the F_4~+ complex should be stable either in a rectangular or in a linear conformation, with dissociation energies of the order of 13-16 kcal/mol.
机译：基于简单分子轨道模型的定性考虑表明，相对于与F_2和F_2〜+片段的离解，自由基阳离子配合物F_4〜+应该是稳定的，具有显着的键能。确实在从头算起MP2级别具有矩形最小值，而线性构形器则具有围绕中心F-F键几乎自由旋转的特征。然而，随着扰动阶数的增加，Moller-Plesset结果不一致且收敛性很差，并且受到非常强烈的自旋污染，并带有线性构象异构体破坏局部对称性的其他问题。二次配置相互作用或耦合簇类型的高级计算，包括单次和两次激发以及三元组的扰动处理（QCISD（T）和CCSD（T）），以其自旋无限制和自旋受限的形式进行。所有高级计算均产生了彼此一致的优化几何形状和键合能，并得出了可靠的结论，即F_4 + +络合物在矩形或线性构象下均应稳定，解离能为13量级。 -16 kcal / mol。

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