A direct comparison between structure correlations and reaction paths

被引:26
作者
Hankinson, DJ [1 ]
Almlof, J [1 ]
Leopold, KR [1 ]
机构
[1] UNIV MINNESOTA,DEPT CHEM,MINNEAPOLIS,MN 55455
关键词
D O I
10.1021/jp960353d
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Reaction paths for the formation of the donor-acceptor complexes HCN-BF3 and H3N-BF3 have been calculated by ab initio methods. The results are compared with the experimentally observed correlation between the B-N bond length and NBF angle for a series of BF3 complexes with amine and nitrile donors. Radial potential functions for the HCN and NH3 complexes exhibit a single minimum, confirming that the large gas-solid structure differences observed in these systems do not arise from distinct isomeric forms. In the case of HCN-BF3, the ab initio results are combined with published vapor pressure data to obtain a value for the molar lattice energy of the crystal. Dipole moments are calculated as a function of B-N separation for both species, and for HCN-BF3, the dipole-dipole interaction energy between adjacent monomers in the solid is shown to comprise a significant portion of the lattice energy. A simple model is described for reproducing the experimentally observed structure correlation among BF3 complexes with nitrogen donors.
引用
收藏
页码:6904 / 6909
页数:6
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