화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.104, No.45, 10534-10542, 2000
Model structures and electron density distributions for the silica polymorph coesite at pressure: An assessment of OO bonded interactions
The crystal structure and the bond critical point, bcp, properties of the electron density distribution for the high-pressure silica polymorph coesite were generated for pressures up to similar to 17 GPa, using first-principles calculations. The nonequivalent SiO bond lengths and the SiOSi and OSiO angles of the generated structures agree with those observed to within similar to1%. With compression, the SiO bond lengths and the variable SiOSi angles of the structures both decrease while the value of the electron density, p(r(c)), the curvatures, and the Laplacian of the electron density distribution at the bond critical points each increases slightly. As found in a recent modeling of the structure of low quartz, the calculated electron density distributions are nearly static and change relatively little with compression. The bcp properties of the model structure agree with those observed at ambient conditions to within similar to 10%, on average, with several of the properties observed to correlate with the observed SiO bond lengths, R(SIO). This agreement is comparable with that observed for several other silicates. As predicted, the bonded radius of the oxide anion, the curvatures of p(r(c)) paralleling the bond paths and the Laplacian of p(r(c)) each correlates with the observed bond lengths. However, the observed p(r(c)) values and the curvatures of p(r(c)) perpendicular to the paths fail to show a correlation with the observed bond lengths. The ellipticity of the SiO bonds in both the model and the observed structures tends to decrease in value as the SiOSi angle approaches 180 degrees, indicating that the bonds become more circular in cross sections as the angle widens. Ridges of electron density and bond critical points were found between the intertetrahedral oxide anions at each pressure. The existence of these features appears to be closely related to purely geometrical factors of the coesite structure rather than to bonded interactions. None of these features was found between the intratetrahedral oxide anions.