Correlation of O-H Stretching Frequencies and O-H centre dot centre dot centre dot O Hydrogen Bond Lengths in Minerals

摘要

A correlation of O-H stretching frequencies (from infrared spectroscopy) with O centre dot centre dot centre dot O and H centre dot centre dot centre dot O bond lengths (from structural data) of minerals was established. References on 65 minerals yielded 125 data pairs for the d (O centre dot centre dot centre dot O)-v correlation; due to rare or inaccurate data on proton positions, only 47 data pairs were used for the d (H...O)-v correlation. The data cover a wide range of wavenumbers from 1000 to 3738 cm~(-1) and O centre dot centre dot centre dot O distances from 2.44 to 3.5 A. They originate from silicates, (oxy) hydroxides, carbonates, sulfates, phosphates, and arsenates with OH~, H_2O, or even H_3O_2~ units forming very strong to very weak H bonds. The correlation function was established in the form v (cm~(-1))=3592-304 centre dot 10~9 centre dot exp (-d (O centre dot centre dot centre dot O)/0.1321), R~2=0.96. Becausr of deviations from ideal straight H bonds, i.e. bent or bifurcated geometry, dynamic proton behavior, but also due to factor group splitting and cationic effects, data scatter considerably around the regression line. The trends of previous correlation curves and of theoretical considerations were confirmed.