RESUMO
Using a pulsed Stern-Gerlach deflection experiment, we present the results of a comparative study on the magnetic properties of neutral sodium-doped solvent clusters Na(Sol)n with n = 1-4 (Sol: H2O, NH3, CH3OH, CH3OCH3). Experimental deflection ratios are compared with values calculated from molecular dynamics simulations. NaNH3 and NaH2O are deflected as a spin 1/2 system, consistent with spin transitions occurring on a time scale significantly longer than 100 µs. For all other clusters, reduced deflection is observed. The observed magnetic deflection behavior is correlated to the number of thermally populated rotational states in the clusters. We discuss that spin-rotational couplings allow for avoided crossings and a reduction in the effective magnetic moment of the cluster. This work attempts to understand the evolution of magnetic properties in isolated weakly bound clusters and is relevant to diamagnetic and paramagnetic species expected to exist in solvated electron systems.
RESUMO
Photoelectron velocity map imaging of Li(CH3OCH3) n clusters (1 ≤ n ≤ 175) is used to search for magic numbers related to the photoelectron anisotropy. Comparison with density functional calculations reveals magic numbers at n = 4, 5, and 6, resulting from the symmetric charge distribution with high s-character of the highest occupied molecular orbital. Since each of these three cluster sizes correspond to the completion of a first coordination shell, they can be considered as "isomeric motifs of the first coordination shell". Differences in the photoelectron anisotropy, the vertical ionization energies and the enthalpies of vaporization between Li(CH3OCH3) n and Na(CH3OCH3) n can be rationalized in terms of differences in their solvation shells, atomic ionization energies, polarizabilities, metal-oxygen bonds, ligand-ligand interactions and by cooperative effects.