Relationship between the Angular Characteristics of a H-bond and the Energetics of Proton Transfer Occurring Within

Authors

Steve Scheiner, Utah State UniversityFollow

Document Type

Article

Journal/Book Title

Journal of Molecular Structure

Publication Date

9-1988

Publisher

Elsevier

Volume

177

First Page

79

Last Page

91

Abstract

Foranumber of differentH-bonded complexes, theprotontransferpotential is computed by ab initio methods for the optimal geometry as well as for variousangulardistortions. In all cases, it is found thatarocking of one subunitAso as to turn its dipole moment away from the other subunit B causes the equilibrium position of theprotonto shift towardA, even if B hasahigherprotonaffinity thanA. This shift may be explained on the basis ofabetter charge-dipole attraction in the preferred AH··B configuration as compared toA··HB. This principle is straightforward for the N bases where the dipole moment is approximately coincident with the N lone pair. The presence of two O lone pairs, neither of which points along the direction of the molecular dipole moment, addsa second factor which results ina net magnification of the above rule.

Comments

http://www.sciencedirect.com/science/article/pii/0022286088800802

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Recommended Citation

Relationship between the Angular Characteristics of a H-bond and the Energetics of Proton Transfer Occurring Within S. Scheiner J. Mol. Struct., 1988 177, 79-91.