Mp. Anisimov et al., RELATIONSHIP OF PHASE-DIAGRAMS AND SURFACES OF NEW PHASE NUCLEATION RATES, The Journal of chemical physics, 109(4), 1998, pp. 1435-1444
Experimental and theoretical investigations of vapor nucleation began
about 100 years ago. Until the 1980s, experiments generally measured o
nly critical supersaturation values. Since then, measurement procedure
s have substantially improved and nucleation rates can now be measured
as a function of temperature, vapor activities, and pressure with hig
h accuracy. Nucleation theory has made obvious progress, but the under
standing of nucleation phenomenon is far from complete. New approaches
to conceptualizing nucleation are necessary in order to identify poss
ible new directions for further improvement of nucleation theory. One
such approach is the analysis of the topology of nucleation rate surfa
ces. The creation of a nucleation rate surface is based on knowledge o
f phase equilibrium diagrams, limited experimental nucleation results,
and a few plausible assumptions. In this article, the surfaces of the
nucleation rates as a function of pressure or activity for single and
binary systems for nucleation from metastable vapor, liquid, and crys
talline states are constructed. : By using surface topology analysis,
some problems in nucleation theory are more clearly formulated and fut
ure directions for improvement can be found. Currently, it is not poss
ible to create a universal nucleation theory based only on first princ
iples. Partial theoretical success can be obtained only in the case of
systems With well-known; molecular interaction potentials. By scaling
the experimental nucleation rate surfaces for portions of the phase d
iagrams that are identical to one another, a semiempirical nucleation
rate surface for an unknown system can be created from its phase diagr
am. Scaling should give quantitative nucleation rates. Phase diagrams
must be more fully incorporated into the interpretation of experimenta
l nucleation results and nucleation theory development. (C) 1998 Ameri
can Institute of Physics.