Results of ab initio molecular orbital (MO) calculations provide a basis for the interpretation of structural and thermodynamic properties of crystals, glasses, and melts containing tetrahedrally coordinated Si, Al, and B. Calculated and experimental tetrahedral atom-oxygen (TO) bond lengths are in good agreement and the observed average SiO and AlO bond lengths remain relatively constant in crystalline, glassy, and molten materials. The TOT framework geometry, which determines the major structural features, is governed largely by the local constraints of the strong TO bonds and its major features are modeled well by ab initio calculations on small clusters. Observed bond lengths for non-framework cations are not always in agreement with calculated values, and reasons for this are discussed in the text. The flexibility of SiOSi, SiOAl, and AlOAl angles is in accord with easy glass formation in silicates and aluminosilicates. The stronger constraints on tetrahedral BOB and BOSi angles, as evidenced by much deeper and steeper calculated potential energy versus angle curves, suggest much greater difficulty in substituting tetrahedral B than Al for Si. This is supported by the pattern of immiscibility in borosilicate glasses, although the occurrence of boron in trigonal coordination is an added complication. The limitations on glass formation in oxysulfide and oxynitride systems may be related to the angular requirements of SiSSi and Si(NH)Si groups. Although the SiO and AlO bonds are the strongest ones in silicates and aluminosilicates, they are perturbed by other cations. Increasing perturbation and weakening of the framework occurs with increasing ability of the other atom to compete with Si or Al for bonding to oxygen, that is, with increasing cation field strength. The perturbation of TOT groups, as evidenced by TO bond lengthening predicted by MO calculations and observed in ordered crystalline aluminosilicates, increases in the series Ca, Mg and K, Na, Li. This perturbation correlates strongly with thermochemical mixing properties of glasses in the systems SiO2-M 1 /+ AlO2 and SiO2-M n+O n/2 (M=Li, Na, K, Rb, Cs, and Mg, Ca, Sr, Ba, Pb), with tendencies toward immiscibility in these systems, and with systematics in vibrational spectra. Trends in physical properties, including viscosity at atmospheric and high pressure, can also be correlated.