화학공학소재연구정보센터
Journal of Chemical Physics, Vol.108, No.20, 8626-8639, 1998
How do quantum effects change conclusions about heterogeneous cluster behavior based on classical mechanics simulations?
Comparisons of classical and quantum Monte Carlo simulation of SF6-(Ar)(n) and SF6-(Ne)(n) clusters are used to examine whether certain novel types of behavior seen in classical simulations of SF6-(Ar)(n) and SF6-(Kr)(n) persist when quantum effects are taken into account. For mixed clusters formed from Ar (and presumably other heavy partners) quantum effects have little effect on calculated properties, even at very low temperatures, so the cluster-size-dependent preference for solvation vs phase separation and "reverse melting" behavior found in the classical simulations may be expected to occur in many heterogeneous systems. On the other hand, quantum effects substantially lower the melting temperatures of clusters formed with Ne, and (except for a couple of unusually stable stacked isomers) effectively remove the barriers separating the maximally-solvated and phase-separated forms, implying that the latter will normally not exist. Moreover, for (at least) the SF6-(Ne)(11) species, when quantum effects are taken into account there is little evidence of solidlike behavior down to the lowest temperatures accessible to our simulation (0.4 K), although classical simulations show a sharp freezing transition at 1.5(+/-0.1) K. Inclusion of three-body triple-dipole Axilrod-Teller-Muto interactions in the overall potential energy has little effect on either quantum or classical Ne cluster simulations.