The basic building blocks of crystalline and
amorphous phosphates are the P-tetrahedra that
result from the formation of sp3 hybrid orbitals by
the P outer electrons (3s23p3). The ®fth electron is
promoted to a 3d orbital where strong p-bonding
molecular orbitals are formed with oxygen 2p
electrons These tetrahedra link
through covalent bridging oxygens to form various
phosphate anions. The tetrahedra are classi®ed
using the Qi terminology [17], where ÔiÕ represents
the number of bridging oxygens per tetrahedron
(shown schematically in Fig. 1). The networks of
phosphate glasses can be classi®ed by the oxygen-
to-phosphorus ratio, which sets the number of
tetrahedral linkages, through bridging oxygens,
between neighboring P-tetrahedra [2].
Zachariasen [18] identi®ed vitreous P2O5 as one
of the prototypical Ôrandom networkÕ glass form-
ers. Indeed, recent diraction studies of v-P2O5,
described below, are consistent with the Zacha-
riasen description of an open, distorted network of
Q3 tetrahedra. Hagg [19], however, challenged
ZachariasenÕs idea that glass forming tendency
relied upon the development of a random, three-
dimensional network, using the metaphosphate
composition as an example of glass formation in
which a large one-dimensional ÔmolecularÕ group
(based on Q2 tetrahedra) inhibits crystallization.
The chromatography studies of Van Wazer [2] and
others since have reinforced the utility of the de-
scription of phosphate glass structures in terms of
distributions of molecular species such as those
proposed by Hagg.
These two descriptions of glass structure are not
incompatible; both predict local bonding similari-
ties in glasses and crystals of identical composi-
tion. (That is, a metaphosphate glass and crystal
will both have structures based on linkages of Q2
tetrahedra.) More importantly for the present re-
view, these two models also illustrate the need to
describe Ôglass structureÕ at dierent length scales.
Having information about the local bond ar-
rangements of the glass forming (or modifying)
polyhedra will not necessarily complete the de-
scription of a glass structure. That short-range
information (generally de®ned by the immediate