Quantum-chemical simulation of the adsorption-induced reduction of strength of siloxane bondsстатья

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1. Полный текст article Flyagina2019_Article_Quantum-chemicalSimulationOfTh.pdf 2,1 МБ 16 мая 2019 [irina.fliagina@gmail.com]

[1] Flyagina I. S., Malkin A. I., Dolin S. P. Quantum-chemical simulation of the adsorption-induced reduction of strength of siloxane bonds // Journal of Molecular Modeling. — 2019. — Vol. 25, no. 161. Mechanical strength of silicate glasses is known to decrease markedly due to the adsorption of molecules from the environment,especially in aqueous alkali solutions. This effect, known as the adsorption-induced reduction of strength (AIRS), has not yetbeen fully understood. Here, the dependence on the chemical nature and electronic properties of adsorbates of the AIRS ofsiloxane bonds in silica was studied by means of quantum-chemical calculations at the wB97X-D3/def2-TZVP level of theory.A siloxane bond was modelled by H3Si-O-SiH3and (HO)3Si-O-Si(OH)3clusters, and the AIRS was simulated by a linear tensiledeformation of the siloxane bond in the presence of the following adsorbates: OH−,Cl−,H2O, H+and H3O+. Potential energyprofiles and derivative force curves of the siloxane bond rupture were obtained. The varying effect of the adsorbates on theenergy-force characteristics of the AIRS can be explained by changes in the bond lengths and electron occupancy. It is shown thatthe AIRS of the siloxane bonds increases with an increase in the nucleophilicity of the adsorbates, and correlates with anadsorbate-induced redistribution of electron density. [ DOI ]

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