Empirical corrections for anharmonic zero-point vibrations of hydrogen and deuterium in geometric hydrogen bond correlations

• DOI: 10.1016/j.molstruc.2004.03.006
• Publication Date: 2004-04-13T10:22:09Z
• Authors: Hans-Heinrich Lim...; Mariusz Pietrzak; Hans Benedict; Peter M. Tolstoy; Nikolai S. Golubev; Gleb S. Denisov
• Keywords: 01 natural sciences; 0104 chemical sciences

Abstract In this paper, empirical corrections for anharmonic ground-state vibrations of hydrogen and deuterium in the hydrogen bridges A–L⋯B, L=H, D are introduced into the geometric hydrogen bond correlation analysis based on the empirical Pauling valence bond orders. The method is verified using the examples of the hydrogen bonded anions in [(CO) 5 Cr–CN⋯H⋯NC–Cr(CO) 5 ] − As(Ph) 4 + ( 1h ), in [(CO) 5 Cr–CN⋯H⋯NC–Cr(CO) 5 ] − N( n -propyl) 4 + ( 2h ), in the model system [CN⋯H⋯NC] − Li + ( 3h ), and their deuterated isotopologs ( 1d , 2d and 3d ) studied previously by dipolar NMR and theoretical methods by H. Benedict et al. [J. Am. Chem. Soc. 120 (1998) 2939]. The new corrections are able to describe isotope effects on hydrogen bond geometries from the weak to the strong hydrogen bond regime, taking into account single and double-well situations.