Department of Chemistry, Michigan Technological University, 1400 Townsend Drive, Houghton, Michigan 49931, USA.
J Phys Chem A. 2011 Sep 29;115(38):10596-9. doi: 10.1021/jp202968n. Epub 2011 Sep 7.
A new stable structure has been found for the anion clusters of hydrogen fluoride. The ab initio method was used to optimize the structures of the (HF)(3)(-), (HF)(4)(-), (HF)(5)(-), and (HF)(6)(-) anion clusters with an excess "solvated" electron. Instead of the well-known "zig-zag" (HF)(n)(-) structure, a new form, (HF)(n-1)F(-)···H, was found with lower energy. In this new form, the terminal hydrogen atom in the (HF)(n)(-) chain is separated from the other part of the cluster and the inner hydrogens transfer along the hydrogen bonds toward the outside fluoride. The negative charge also transfers from the terminal HF molecule of the chain to the center fluoride atoms. The (HF)(n)(-) clusters for n = 4, 5, and 6 have not yet been observed experimentally. These results should assist in the search for these systems and also provide a possible way to study the proton and electron transfer in some large hydrogen bonding systems.
已发现氟化氢阴离子簇的新稳定结构。使用从头算方法优化了过量“溶剂化”电子的（HF）（3）（-）、（HF）（4）（-）、（HF）（5）（-）和（HF）（6）（-）阴离子簇的结构。与众所周知的“之字形”（HF）（n）（-）结构相反，发现了一种新的形式（HF）（n-1）F（-）···H，其能量更低。在这种新形式中，（HF）（n）（-）链中的末端氢原子与簇的其他部分分离，并且内部氢沿着氢键向外部氟转移。负电荷也从链末端的 HF 分子转移到中心氟原子。n = 4、5 和 6 的（HF）（n）（-）簇尚未在实验中观察到。这些结果应该有助于寻找这些系统，并为研究某些大氢键系统中的质子和电子转移提供一种可能的方法。
