The Mössbauer spectra of trigonal
α-FePO4, measured between 4.2 and 300 K, exhibit
hyperfine parameters characteristic of high-spin iron(III) in a pseudotetrahedral
oxygen environment. Between 24.5 and 300 K, the spectra show a paramagnetic
quadrupole doublet and at 24.0 K the spectrum reveals the onset of
antiferromagnetic exchange. At 4.2 and 16 K, a single magnetic sextet
is observed with hyperfine fields of 51.36(1) and 42.74(1) T, respectively,
with an angle, θ, of 90° between the principal axis of
the electric field gradient tensor in the basal plane of the trigonal
unit cell and the hyperfine field along the c axis.
The spectra obtained between 21 and 18 K have been fitted with two
equal-area magnetic sextets with θ angles of 25 and 85°,
angles which indicate that the iron(III) magnetic moments are canted
away from the c axis. The reduced hyperfine field
versus reduced temperature plot indicates a departure from a Brillouin S = 5/2 behavior, as a result of some magnetostriction at
the Néel temperature. The Mössbauer spectra of class
1 mixed-valence SrFe3(PO4)3, measured
between 4.2 and 300 K, exhibit hyperfine parameters characteristic
of two high-spin iron(II) ions and one high-spin iron(III) ion in
a pseudooctahedral oxygen environment. At and above 40 K, the spectra
show two paramagnetic quadrupole doublets, whereas at 39.0 K the spectrum
reveals the onset of ferrimagnetic exchange. Between 4.2 and 30 K,
the spectra have been fitted with two magnetic sextets with θ
angles of 85 and 10° for the iron(II) and iron(III) sites, respectively.
The reduced hyperfine field versus reduced temperature plots for the
iron(II) and iron(III) sites show a distinct departure from Brillouin S = 2 and S = 5/2 behavior, respectively,
a departure that suggests a first-order magnetic transition at 39.5(5)
K with differing magnetostrictions at the iron(II) and iron(III) sites.