The Sign and Magnitude of 2hJ(F,F) and 1hJ(F,H) in FH···FH. A CLOPPA Analysis of Their Distance Dependence
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- 作者：Claudia G. Giribet ; Martí ; n C. Ruiz de Azú ; a
- 刊名：Journal of Physical Chemistry A
- 出版年：2006
- 出版时间：October 12, 2006
- 年：2006
- 卷：110
- 期：40
- 页码：11575 - 11583
- 全文大小：182K
- 年卷期：v.110,no.40(October 12, 2006)
- ISSN：1520-5215
文摘
The sign change of the intermolecular 2hJ(F,F) coupling in the (HF)2 dimer as a function of the F-F distanceis discussed by means of the CLOPPA method. It is found that it is due to the competition of positive andnegative contributions involving the interaction of the 
lone pair of the acceptor nucleus with vacant molecularorbitals localized in the F-H···F moiety and with other molecular orbitals localized in the donor molecule.The origin of the sign of each contribution is fully determined by analyzing the response of the electronicsystem to the magnetic perturbation at the acceptor F nucleus. 2hJ(F,F) coupling in the FH···F-, which ispositive for all F-F distances, is also analyzed in order to look for the differences with the former case.
lone pair of the acceptor nucleus with vacant molecularorbitals localized in the F-H···F moiety and with other molecular orbitals localized in the donor molecule.The origin of the sign of each contribution is fully determined by analyzing the response of the electronicsystem to the magnetic perturbation at the acceptor F nucleus. 2hJ(F,F) coupling in the FH···F-, which ispositive for all F-F distances, is also analyzed in order to look for the differences with the former case.