Simple bond length dependence: a correspondence between reactive fluid theories.
Two elementary models of reactive fluids are examined, the first being a standard construction assuming molecular dissociation at infinite separation; the second is an open mixture of nondissociative molecules and free atoms in which the densities of free atoms and molecules are coupled. An approximation to the density of molecules, to low order in site density, is derived in terms of the classical associating fluid theory variously described by Wertheim [J. Chem. Phys. 87, 7323 (1987)] and Stell [Physica A 231, 1 (1996)]. The results are derived for a fluid of dimerizing hard spheres, and predict dependence of the molecular density on the total site density, the hard sphere diameter, and the bond length of the dimer. The results for the two reactive models are shown to be qualitatively similar, and lead to equivalent predictions of the molecular density for the infinitely short and infinitely long bond lengths.
Dyer
Kippi M
KM
Chemistry Department, University of Houston, Houston, Texas 77204-5003, USA.
Perkyns
John S
JS
Pettitt
B M
BM
D000465:Algorithms; D003198:Computer Simulation; D044085:Microfluidics / Q000379:methods*; D008956:Models, Chemical; D008958:Models, Molecular; D044367:Phase Transition; D012996:Solutions / Q000737:chemistry*
D012996:Solutions