Like Charges Attract?

Abstract

Using multiscale first-principles calculations, we show that two interacting negatively charged B12I9(-) monoanions not only attract, in defiance of the Coulomb's law, but also the energy barrier at 400 K is small enough that these two moieties combine to form a stable B24I18(2-) moiety. Ab initio molecular dynamics simulations further confirm its stability up to 1500 K. Studies of other B12X9(-) (X = Br, Cl, F, H, Au, CN) show that while all of these B24X18(2-) moieties are stable against dissociation, the energy barrier, with the exception of B24Au18(2-), is large so as to hinder their experimental observation. Our results explain the recent experimental observation of the "spontaneous" formation of B24I18(2-) in an ion trap. A simple model based upon electrostatics shows that this unusual behavior is due to competition between the attractive dipole-dipole interaction caused by the aspherical shape of the particle and the repulsive interaction between the like charges.