The Crystal Structure of α-F2 : Solving a 50 Year Old Puzzle Computationally.
The Crystal Structure of α-F2 : Solving a 50 Year Old Puzzle Computationally.
复制标题
α-F2 的晶体结构：通过计算解决 50 年前的难题
作者：
S. Mattsson;B. Paulus;F. A. Redeker;H. Beckers;S. Riedel;C. Müller
采用增量法计算了具有C2/c空间群对称性的α-氟原子在基准质量下的结合能。已知的实验X射线结构数据需要改进，因为报告的分子内键长不切实际地大。在CCSD（T）水平上，包括零点能修正、基组叠加误差，并外推到完整基组极限，计算出的内聚能为−8.72 kJ mol− 1，与0 K外推的实验值−8.35 kJ mol−1非常吻合。 将C2/c结构与氯、溴和碘的Cmc结构进行比较，发现与较重的卤素相比，固体氟的不同结构的起源是缺乏显著稳定的σ-空穴相互作用。此外，在耦合团簇水平上计算了固态氟中伸缩模的波数，并与新记录的凝聚态氟的拉曼光谱进行了比较。实验和计算都表明，相对于气相中的自由F2分子，拉伸模式分别轻微上移2或5 cm−1。
The cohesive energy of α‐fluorine, withC2/cspace group symmetry, was calculated at benchmark quality by applying the method of increments. The known experimental X‐ray structure data needed to be refined, since the reported intramolecular bond length was unrealistically large. At the CCSD(T) level, including corrections for zero‐point energy, the basis set superposition error, and extrapolated to the complete basis set limit, a cohesive energy of −8.72 kJ mol−1was calculated, which agrees well with the 0 K‐extrapolated experimental value of −8.35 kJ mol−1. Comparison of theC2/cstructure with aCmcastructure, isotypic to that of chlorine, bromine, and iodine reveals that the origin of the different structure of solid fluorine, compared to the heavier halogens, is the lack of significantly stabilizing σ‐hole interactions. In addition, the wave numbers of the stretching mode in solid fluorine were calculated at coupled cluster level and compared to newly recorded Raman spectra of condensed fluorine. Both experiment and calculation indicate a slight up‐shift for the stretching mode by 2 or 5 cm−1, respectively, with respect to a free F2molecule in the gas phase.
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增量修正周期性局部 MP2 计算：I 分子晶体的内聚能
影响因子：
5.5
作者：
C. Müller;D. Usvyat
通讯作者：
D. Usvyat
α-氟的晶体结构
DOI：
10.1063/1.1670323
发表时间：
1968
期刊：
The Journal of chemical physics
影响因子：
--
作者：
L. Meyer;C. Barrett;S. C. Greer
通讯作者：
S. C. Greer
氟的拉曼光谱
影响因子：
4.4
作者：
D. Andrychuk
通讯作者：
D. Andrychuk
影响因子：
1.7
作者：
B. M. Powell;K. Heal;B. Torrie
通讯作者：
B. M. Powell;K. Heal;B. Torrie
影响因子：
5.5
作者：
Cervinka, Ctirad;Fulem, Michal
通讯作者：
Fulem, Michal