The only truly unique PDF information is about *correlations*.  Let's say
you have two bonded sites, both with anisotropic thermal ellipsoids along
the bond, and let's assume that the motion is purely harmonic.  A sharp PDF
peak will indicate that the atoms move predominanly in-phase, a broad PDF
peak that the atoms move predominantly out-of-phase.  The two scenarios will
give identical Fourier maps as reconstructed from the Bragg peaks, whatever
the Qmax, so the additional width (or additional narrowness) of the peak
with respect to an uncorrelated model arises purely from the non-Bragg
scattering.  You can make the same argument for static correlations.
Ga(1-x)In(x)As is a typical case.  It is not a split-site problem, in that
both Ga/In and As will be slightly displaced locally depending on their
surrounding, but the displacements are correlated in such a way as to give a
shorter bond length for Ga-As and a longer one for In-As.
Of course, PDF is also used to look at more general issues of static/dynamic
disorder that could also be examined using Bragg scattering, and in many
case it does quite well.  PDF is not (yet) very good for structural
refinements (so it is to be used only in desperate cases of highly
disordered systems) and is pretty hopeless for weak ordered displacement
patters, since the extra Bragg peaks in crystallography "lock-in" on the new
modulation even in the presence of large unrelated displacements.   For this
very reason, PDF tends to miss phase transitions, particularly at higher
temperatures, which led to some very wierd claims in the past literature.
There is a lot of controversy about PDF being able to say something about
weak disordered displacement patters (e.g., dynamic stripes), but I am
personally very skeptical.  PDF requires exquisite data and a true passion
for data analysis.  If you have a good problem, you can get (probably) the
best PDF data worldwide "almost" routinely on my instrument GEM at the ISIS
facility (see also the cited paper by Billinge).

Paolo Radaelli

Reply via email to