2D-3D Structural Transition in B12Fn (n=0-7)

来源 :第七届国际理论化学、分子模拟和生命科学研讨会暨科学计算和模拟软件发展平台学术交流会 | 被引量 : 0次 | 上传用户:whxust
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  An ab initio investigation performed in our previous work [1] indicates that the perfectly planar D3h B12H6 (the so-called borozene) proposed by Szwacki et al in 2009 [2] is a high-lying local minimum of the system.In 2012,the same group claimed that the fluorinated borozene D3h B12F6 (14) would be more stable than its three-dimensional counterpart Cs B12F6 (13) at B3LYP.We doubt if it is true based upon our previous experience.Extensive density functional and wave function investigations performed in this work shows that,although the perfectly planar D3h B12F6 (14) lies 14.5 kcal/mol lower than the cage-like C2 B12F6 (13) at B3LYP,it proves to be 14 kcal/mol less stable than the latter at the more accurate coupled-cluster level with triple excitation (CCSD(T)) (see Fig.1 and Fig.2).Furthermore,a planar(2D)-to-icosahedral(3D) structural transition occurs to B12Fn between n=4-5,again,similar to B12Hn.[1] We conclude that a partial fluorination can not overturn the relative stability of boron hydride clusters and,similar to D3h B12H6,the planar fluorinated B12F6 (14) is just a high-lying local minimum of the system almost impossible to be produced in experiments.The true global minimum of B12F6(13) remains icosahedral,similar to the 3D B12H6.
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