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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >An atoms in molecules and electron localization function computational study on the molecular structure of the 6-tricyclo[3.2.1.0~(2,4)]octyl cation
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An atoms in molecules and electron localization function computational study on the molecular structure of the 6-tricyclo[3.2.1.0~(2,4)]octyl cation

机译：分子中的原子与6-三环[3.2.1.0〜（2,4）]辛基阳离子分子结构的电子定位功能计算研究

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The structure of 6-tricyclo[3.2.1.0~(2,4)]cation 1 was optimized at HF,Becke3PW91,Becke3LYP,MP2,and MP2(full)levels with the 6-31G(d,p) basis set.Becke3PW91 and MP2(full)yislded similar values for the geometrical parameters of optimized 1.When the C4-C6 distance was changed incrementally through the range 1.40-2.32A at the Becke3PW91/6-311G(d,p)level,there was no dicontinuity in the total energy and the geometrical parameters of the cyclopropyl group underwent marked changes.AIM(the theory of atoms in molecules)and ELF(electron localization function)analyses were carried out to investigate the molecular structure of 1.No bond path was found between C4 and C6 so 1 is a classical cation without pentacoordinated carbon atoms.Only when the C4-C6 distance was fixed in the range of 1.50-1.62A does 1 become a pentacorrdinate(nonclassical)species in which C4 is connected to C2,C3,C5,C6 and H13 with bond paths.On the other hand,when the 6-tricyclo[3.2.1.0~(2,4)]octyl cation was substituted with Li and BeH groups at C4 and C5,the optimized equilibrium species exhibted pentacoordinate carbons at C4.Compared with the C1-C2 bond that we take as a normal single bond,the bonds between C4 and C2,C3,C5are weak,as evidenced by reduced densities #rho#(r),significantly smaller triangle open~2#rho#(r) values,and large ellipticities at the bond critical points (BCPs).The delocalization indices (DIs)-the first application of a DI analysis in the study of carbocations-for these C-C bonds ranged between 0.733 and 0.860,smaller than unity.The DI between C4 and C6 is 0.634,suggesting that there is a significant degree of homoconjugation between C4 and C6.For polycyclic species such as 1,it appears that a delocalization index of approximately 0.7 and an internuclear distance of 1.6A are required for a bond path to materialize between remote carbons.In an ELF analysis we found a small disynaptic basin V(C4,C6)between C4 and C6 that correlated with the existence of a(3,-1)critical point in -triangle open~2#rho#(r).The properties of ELF disynaptic basins around C4 and a contribution analysis showed a high degree of delocalization at this center.
机译：6-三环[3.2.1.0〜（2,4）]阳离子1的结构在HF，Becke3PW91，Becke3LYP，MP2和MP2（full）水平下以6-31G（d，p）为基础进行了优化。在最佳1的几何参数上，MP2（全）的值相似。当在Becke3PW91 / 6-311G（d，p）水平上C4-C6距离在1.40-2.32A范围内递增变化时，不存在连续性在总能量和环丙基的几何参数上发生了显着变化。进行了分子内原子理论（AIM）和电子定位功能（ELF）分析以研究1的分子结构。 C4和C6 so 1是没有五配位碳原子的经典阳离子。只有当C4-C6距离固定在1.50-1.62A范围内时，1才成为五碳素（非经典）物种，其中C4连接到C2，C3， C5，C6和H13具有键路径。另一方面，当6-三环[3.2.1.0〜（2,4）]辛基阳离子被C4和C5处的Li和BeH基团，最优化的平衡物种在C4处释放出五配位碳。与我们将C1-C2键作为普通单键相比，C4和C2，C3，C5之间的键较弱，证明降低密度＃rho＃（r），大大减小的三角形开孔〜2＃rho＃（r）值以及键临界点（BCP）的大椭圆率。离域指数（DI）-DI分析的第一个应用是对这些碳键的碳正离子的研究范围为0.733至0.860，小于1。C4和C6之间的DI为0.634，这表明C4和C6之间存在显着的共轭程度。对于多环物种，例如1，似乎在离键碳之间形成键合路径需要约0.7的离域指数和1.6A的核间距。在ELF分析中，我们发现C4和C6之间的一个小的突触盆地V（C4，C6）与-tria中存在（3，-1）临界点ngle open〜2＃rho＃（r）。C4周围的ELF突触盆地的性质和贡献分析表明，该中心高度散布。

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