Abstract
Ab initio, molecular orbital calculations have been performed on a variety of hypothetical aluminosilicate molecules to investigate relationships among composition, structure, and infrared spectra of OH. Vibrational analyses of the full-optimized molecular geometries at the 3–21G** level were performed with Gaussian 92 to determine theoretical infrared spectra. Theoretical infrared OH frequencies, ν(OH), shift 10 to 100 cm−1 with ionic substitutions. The inverse correlation of theoretical infrared OH intensities with OH stretching frequencies in these aluminosilicate molecules is similar to that observed for aluminosilicate glasses (Paterson 1982). O-H bond lengths, H-bond distances, and H⊗nd angles correlate with frequency. The dominant factor affecting ν(OH) is the H-bond distance, if this distance is less than 2 Å. Beyond H-bond distances of 2 Å, structural and compositional effects exert competitive influences on ν(OH).
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Kubicki, J.D., Sykes, D. & Rossman, G.R. Calculated trends of oh infrared stretching vibrations with composition and structure in aluminosilicate molecules. Phys Chem Minerals 20, 425–432 (1993). https://doi.org/10.1007/BF00203113
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DOI: https://doi.org/10.1007/BF00203113