期刊
MOLECULAR PHYSICS
卷 109, 期 20, 页码 2451-2460出版社
TAYLOR & FRANCIS LTD
DOI: 10.1080/00268976.2011.620026
关键词
halogen bond; QTAIM; NBO; cooperative effects; EDA
A theoretical study was performed to examine intermolecular halogen bond properties in one-dimensional NCX chains (X = Cl and Br). Geometries, binding energies, and n(N) -> sigma*(C-X) charge-transfer of linear (NCCl)(2-10) and (NCBr)(2-10) chains were investigated by means of second-order Moller-Plesset perturbation theory (MP2) and DFT methods. All MP2, B3LYP and M06/aug-cc-pVTZ results indicate that the magnitudes of the interaction energies increase with increasing halogen size. Considering MP2/aug-cc-pVTZ results, it can be seen that the (NCBr)(10) cluster is bound -12.72 kcal/ mol more strongly than (NCCl)(10). The n-dependent trend of nN -> sigma*(C-X) charge-transfer is reasonably correlated with cooperative effects in halogen bond energies. According to the quantum theory of atoms in molecules, the capability of the (NCX)(2-10) clusters for electron localization, at the C-X . . . N bond critical point (BCPs), depends on the cluster size and thereby leads to cooperative changes in the C-X . . . N strength, and n(N) -> sigma*(C-X) charge-transfer. It is also revealed that for all intermolecular C-X . . . N interactions, total electronic energy densities are all greater than zero, suggesting that the interactions are significantly electrostatic in nature.d
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据