期刊
JOURNAL OF THEORETICAL & COMPUTATIONAL CHEMISTRY
卷 8, 期 4, 页码 615-629出版社
WORLD SCIENTIFIC PUBL CO PTE LTD
DOI: 10.1142/S0219633609004964
关键词
Halogen bonding; weak interaction; atoms in molecules; symmetry-adapted perturbation theory
资金
- National Natural Science Foundation of China [20673105]
- MOST National Basic Research Program of China [2006CB922004]
- MOST 973 Program [2007CB815204]
The halogen bonding complexes H2O center dot center dot center dot M (M = F-2, ClF, and CF4) in comparison with the hydrogen bonding H2O center dot center dot center dot HF complex are studied by high-level ab initio calculations and electron topological atoms-in-molecules (AIM) analyses. The basis set superposition error corrections are important to predict if the structures are in good agreement with the experimental results. Both the CCSD(T)/aug-cc-pVTZ calculations and the AIM analyses indicate a interaction strength order: H2O center dot center dot center dot HF > H2O center dot center dot center dot ClF > H2O center dot center dot center dot F-2 > H2O center dot center dot center dot CF4, with the interaction energies -7.91, -4.16, -1.11, and -1.05 kcal/mol, respectively. The symmetry-adapted perturbation theory analyses have been carried out towards understanding of the nature of the halogen bonding interactions in the complexes H2O center dot center dot center dot M (M = F-2, ClF, and CF4), where the exchange energies are the predominant repulsive components. For the complexes involving polar monomers, the hydrogen bonding H2O center dot center dot center dot HF and the halogen bonding H2O center dot center dot center dot ClF, the largest attractive contributions are the electrostatic energies. However, in H2O center dot center dot center dot F-2 and H2O center dot center dot center dot CF4, the attractive dispersion energies become more important, and the induction energy in the former complex is a little higher than that in the latter. In contrary to the red-shifts of H-F, Cl-F, and F-F bond stretching vibrational frequencies in the complexes H2O center dot center dot center dot M (M = HF, ClF, and F-2), the blue-shifts are predicted for C-F bonds neighboring water in H2O center dot center dot center dot CF4.
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