Monte Carlo simulations and the hypernetted chain theory are used to study
the interaction between spherical macroions of opposite charge immersed in
a solution of monovalent or divalent simple electrolyte. These calculations
represent the first step toward studying phase behavior and precipitation
kinetics in solutions containing a mixture of macroions with positive and n
egative net charges. The potential of mean force between colloidal particle
s is determined as a function of colloid-colloid separation. In addition to
having an opposite sign, the calculated potential of mean force is found t
o be stronger and longer-ranged than observed in the case of equally charge
d macroparticles. The difference is more pronounced in the presence of diva
lent counterions and is especially noticeable when we compare distinct Coul
ombic and hard-core collision contributions to the interaction between equa
lly and oppositely charged colloids. The present observations suggest the d
ominance of attractive forces between globally neutral but electrostaticall
y heterogeneous macroparticles. While our numerical results cannot be succe
ssfully analyzed by existing theories, they provide useful guidance and ben
chmark data for the development of advanced analytic descriptions.