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Structures and Heats of Formation of Simple Alkaline Earth Metal Compounds II: Fluorides, Chlorides, Oxides, and Hydroxides for Ba, Sr, and Ra

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journal contribution
posted on 14.12.2017, 00:00 by Monica Vasiliu, J. Grant Hill, Kirk A. Peterson, David A. Dixon
Geometry parameters, vibrational frequencies, heats of formation, bond dissociation energies, cohesive energies, and selected fluoride affinities (difluorides) are predicted for the late alkaline earth (Sr, Ba, and Ra) oxides, fluorides, chlorides, and hydroxides at the coupled cluster theory CCSD­(T) level. Additional corrections (scalar relativistic and pseudopotential corrections, vibrational zero-point energies, and atomic spin–orbit effects) were included to accurately calculate the total atomization energies and heats of formation following the Feller–Peterson–Dixon methodology. The calculated values are compared to the experimental data where available. In some cases, especially for Ra compounds, there are no experimental results, or the experimental energetics and geometries are not reliable or have very large error bars. All of the Sr, Ba, and Ra difluorides, dichlorides, and dihydroxides are bent structures with the OMO bond angles decreasing going down the group. The cohesive energies of bulk Be dihalides are predicted to be quite low, while those of Ra are relatively large. The fluoride affinities show that the difluorides are moderately strong Lewis acids and that such trifluorides may form under the appropriate experimental conditions.