Two different lengths of P-O bonds in the PO4 units of phosphate glasses ar
e found by neutron diffraction experiments of high resolution in real spade
. The two lengths are related to bonds of the phosphorus atom with the term
inal and the bridging oxygen atoms. The mean lengths and widths of both P-O
distance peaks change as a function of the glass composition. In a large r
ange, starting from vitreous P2O5 up to the pyrophosphate composition, the
behavior of the bond lengths is compared with that in the related crystals
and with that resulting from ab initio calculations. The bond lengths depen
d not only on the species of the participating oxygen atoms and on the numb
er of links of the concerning PO4 unit but also on the number of links of t
he neighboring PO4 unit and on the species of the modifier cation.