RESUMO
para-Hydrogen (pH2)N clusters have been the focus of numerous computational studies. Originally motivated by the possibility of observing superfluidity, these studies also revealed rich and complex structural properties of (pH2)N. However, their structural analysis was typically limited to attempts to identify "magic number clusters" by computing their ground state energies EN and the chemical potential µN = EN-EN-1 as a function of N. This was followed by structural analysis based on an ill-defined radial density profile. Surprisingly, however, there were remarkable discrepancies between the results reported in the literature for cluster sizes beyond approximately N = 25, and this ambiguity remained unsettled until now. In the present paper, we apply the diffusion Monte Carlo method to resolve inconsistencies in cluster sizes within the range (N = 24-28). Here, we try to avoid speculations based on the highly demanding energy calculations whose numerical accuracy harbors ambiguity. Instead, we focus on the direct and unambiguous structural analysis of the ground state wavefunctions, which supports the conclusion that the clusters are structurally the same in the size range considered. That is, there are no magic number clusters at least in the range N = 24-28, contrary to what some of the previous publications have suggested. This lack of size sensitivity of para-hydrogen clusters is a direct consequence of the strong quantum delocalization in these systems.
RESUMO
The Diffusion Monte Carlo (DMC) method was applied to anionic hydrogen clusters H-(H2)n (n = 1-16, 32) and their deuterated analogs using a polarizable all-atom potential energy surface (PES) developed by Calvo and Yurtsever. For the hydrogen clusters, the binding energy ΔEn appears to be a smooth function of the cluster size n, thus contradicting the previous claim that n = 12 is a "magic number" cluster. The structures of the low energy minima of the PES for these clusters belong to the icosahedral motif with the H2 molecules aligned toward the central H- ion. However, their ground state wavefunctions are highly delocalized and resemble neither the structures of the global nor local minima. Moreover, the strong nuclear quantum effects result in a nearly complete orientational disordering of the H2 molecules. For the deuterium clusters, the ground state wavefunctions are localized and the D2 molecules are aligned toward the central D- ion. However, their structures are still characterized as disordered and, as such, do not display size sensitivity. In addition, DMC simulations were performed on the mixed H-(H2)n(D2)p clusters with (n, p) = (6, 6) and (16, 16). Again, in contradiction to the previous claim, we found that the "more quantum" H2 molecules prefer to reside farther from the central H- ion than the D2 molecules.
