Structure and stability of Ne+He(n): experiment and diffusion quantum Monte Carlo theory with "on the fly" electronic...

New data are reported for the mass-spectrometry fragmentation patterns of helium clusters, either pure or containing a Ne or an Ar atom. The patterns for He(n)+ and Ar+He(n) show clear evidence of structure, while those of Ne+He(n) do not. To better understand the surprising result for the Ne+He(n) fragments, diffusion quantum Monte Carlo (DMC) calculations of the energies and structural properties of these ions were performed using a diatomics-in-molecule (DIM) parametrization of the potential energy. Using DIM for electronic energy evaluation allows us to sample 10(9) configurations even for a cluster as large as Ne+He14. The results of the DMC calculation are very surprising. For n > 7, the DMC random walkers rarely venture within 100 cm(-1) of the minimum potential energy. Analysis of the resulting particle density distributions shows that the zero-point energy does more than spread the wave function around the potential-energy minima, resulting in very diffuse wave functions. For some of the clusters the quantum effects nearly exclude the region of the potential minimum from the overall wave function. An important result of this effect is that the incremental bonding energy of the nth helium atom varies quite smoothly with n, for n > 5. This eliminates the expected shell structure and explains the lack of magic-number-type features in the data.