O-H · O Hydrogen bonds in molecular crystals a statistical and quantum-chemical analysis
1975; Elsevier BV; Volume: 24; Issue: 1 Linguagem: Inglês
10.1016/0022-2860(75)85069-1
ISSN1872-8014
AutoresJ. Kroon, J. A. Kanters, Jeanne G. C. M. van Duijneveldt-van de Rijdt, F. B. van Duijneveldt, J. A. Vliegenthart,
Tópico(s)Various Chemistry Research Topics
Resumo196 hydrogen bonds taken from 45 crystal structures of polyalcohols, saccharides and related compounds have been submitted to a statistical analysis. The resulting histograms for some of the geometrical parameters are interpreted as Boltzmann distributions, and force constants are derived from them. The energy of different O-H ·· O configurations is obtained from ab initio SCF calculations on some 40 near-equilibrium geometries of the (H2O)2 dimer. The observed and calculated results led to the following conclusions. (1) Non-linear H bonds occur frequently because of a trivial geometrical factor together with an energetical preference for non-linearity in most nonoptimal geometries. (2) A distinct preference was neither observed nor calculated for hydrogen bonding in the direction of one of the acceptor lone pairs. (3) Nearly all observed O-H ·· O arrangements have a calculated energy that is less than about l kcal mol −1 above that of the calculated optimum geometry. (4) The range of accessible dimer geometries is largely determined by the classical Coulomb energy.
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