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Hydrogen bonding described through diatomics-in-ionic-systems: The HF dimer
 

Summary: Hydrogen bonding described through diatomics-in-ionic-systems:
The HF dimer
B. L. Grigorenko and A. V. Nemukhin
Department of Chemistry, Moscow State University, Moscow, 119899, Russian Federation
V. A. Apkarian
Department of Chemistry, University of California, Irvine, California 92697-2025
Received 6 October 1997; accepted 15 December 1997
With the proper inclusion of ion-pair configurations, the diatomics-in-molecules formalism can be
used to accurately describe hydrogen bonding. This is demonstrated for the well characterized
prototype, the HF dimer, the structure and entire potential energy surface of which is reproduced
within its known accuracy: At the stationary points potential minimum and saddle points energies
and bond lengths are reproduced with an accuracy of 1%, and the soft hydrogen bond angles are
determined to within 5%. This is accomplished through a minimal basis Hamiltonian--
19-dimensional matrix to describe the planar complex--constructed with analytic fits to accurately
known or determined pair potentials. The construct includes the H F ion-pair states of the HF
monomer units. The three-body nature of the inductive ion-pair interactions with neutrals is
preserved, in the spirit of diatomic-in-ionic-systems. Based on ab initio estimates, in the limited
range of interest, a Gaussian function describes the mixing between ionic and neutral states. The
amplitude of this function is the only adjustable parameter in the model. The ionicity anisotropy and
nonadditivity of interactions, responsible for the structure of the HF dimer, result naturally from

  

Source: Apkarian, V. Ara - Department of Chemistry, University of California, Irvine

 

Collections: Chemistry