Proton–donor properties of water and ammonia in van der Waals complexes with rare‐gas atoms. Kr–H2O and Kr–NH3

Authors

G. Chalasinski
M. M. Szczesniak
Steve Scheiner, Utah State UniversityFollow

Document Type

Article

Journal/Book Title

Journal of Chemical Physics

Publication Date

1992

Volume

97

First Page

8181

Last Page

8187

Abstract

The perturbation theory of intermolecular forces in conjunction with the supermolecular Møller–Plesset perturbation theory is applied to the analysis of the potential‐energy surfaces of Kr–H₂O and Kr–NH₃ complexes. The valleylike minimum region on the potential‐energy surface of Kr–H₂O ranges from the coplanar geometry with the C₂ axis of H₂O nearly perpendicular to the O–Kr axis (T structure) to the H‐bond structure in which Kr faces the H atom of H₂O. Compared to the previously studied Ar–H₂O [J. Chem. Phys. 94, 2807 (1991)] the minimum has more of the H‐bond character. The minimum for Kr–NH₃ corresponds to the T structure only, in accordance to the result for Ar–NH₃ [J. Chem. Phys. 91, 7809 (1989)]. The minima in Kr–H₂O and Kr–NH₃ are roughly 27% and 19%, respectively, deeper than for the analogous Ar complexes. To examine the proton–donor abilities of O–H and N–H bonds the ratios of the deformation energy to dispersion energy are considered. They reflect fundamental differences between the two bonds and explain why NH₃ is not capable of forming the H‐bond structures to rare‐gas atoms.

Comments

Originally published by American Institute of Physics in the Journal of Chemical Physics.

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Recommended Citation

Proton--donor properties of water and ammonia in van der Waals complexes with rare-gas atoms. Kr--H[sub 2]O and Kr--NH[sub 3] G. Chalasinski, M. M. Szczesniak, and S. Scheiner, J. Chem. Phys. 97, 8181 (1992), DOI:10.1063/1.463440