Department of Chemistry, Youngstown State University, Youngstown, Ohio 44555, USA.
J Phys Chem A. 2010 Dec 16;114(49):12958-62. doi: 10.1021/jp110295n. Epub 2010 Nov 16.
Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to determine the structures, binding energies, and bonding of complexes FCl:CNX, with X = CN, NC, NO(2), F, CF(3), Cl, Br, H, CCF, CCH, CH(3), SiH(3), Li, and Na. Equation-of-motion coupled cluster calculations have also been carried out to determine the coupling constants (1)J(F-Cl), (1X)J(Cl-C), and (2X)J(F-C) across these halogen bonds. As the strength of the base is systematically increased, the nature of the halogen bond changes from traditional, to chlorine-shared, to ion-pair. The type of halogen bond present in a complex can be readily determined from its structure, binding energy, AIM bonding analyses, and spin-spin coupling constants. Coupling constants across halogen bonds are compared with corresponding coupling constants across traditional, proton-shared, and ion-pair hydrogen bonds.
已进行从头算 MP2/aug'-cc-pVTZ 计算，以确定复合物 FCl:CNX（其中 X = CN、NC、NO(2)、F、CF(3)、Cl、Br、H、CCF、CCH、CH(3)、SiH(3)、Li 和 Na）的结构、结合能和键合。还进行了运动方程耦合簇计算，以确定这些卤键的耦合常数 (1)J(F-Cl)、(1X)J(Cl-C) 和 (2X)J(F-C)。随着碱强度的系统增加，卤键的性质从传统的、氯共享的到离子对的变化。复合物中存在的卤键类型可以通过其结构、结合能、AIM 键分析和自旋-自旋耦合常数来轻易确定。卤键的耦合常数与传统的质子共享和离子对氢键的对应耦合常数进行了比较。
