Aspects of correlation function realizability
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Jenness Crawford, Salvatore Torquato,a) and Frank H. Stillinger
Department of Chemistry and Princeton Materials Institute,
Princeton University, Princeton, New Jersey 08544
Received: 6 June
2003; accepted: 16 July 2003
The pair-correlation function
g2(r) describes short-range order in many-particle
systems. It must obey two necessary conditions: (i) non-negativity
for all distances r, and (ii) non-negativity of its associated
structure factor S(k) for all k. For the
elementary unit step-function g2 form, previous
work [F. H. Stillinger, S. Torquato, J. M. Eroles, and T. M.
Truskett, J. Phys. Chem. B 105, 6592 (2001)] indicates that
(i) and (ii) could be formally satisfied, but only up to a terminal
density at which the covering fraction of particle exclusion
diameters equaled 2–d in d dimensions. To
test whether the unit step g2 is actually
achievable in many-particle systems up to the apparent terminal
density, a stochastic optimization procedure has been used to shift
particles in large test systems toward this target g2.
Numerical calculations for d = 1 and 2 confirm that the step
function g2 is indeed realizable up to the terminal
density, but with substantial deviation from the configurational
preferences of equilibrium hard-rod and hard-disk models. We show
that lineal statistical measures are particularly sensitive to this
difference. Our results also illustrate the characteristics of
"closest approach" to the step function g2 above
the terminal density.