Probing the presence and absence of metal-fullerene electron transfer reactions in helium nanodroplets by deflection measurements.

Metal-fullerene compounds are characterized by significant electron transfer to the fullerene cage, giving rise to an electric dipole moment. We use the method of electrostatic beam deflection to verify whether such reactions take place within superfluid helium nanodroplets between an embedded C60 molecule and either alkali (heliophobic) or rare-earth (heliophilic) atoms. The two cases lead to distinctly different outcomes: C60Nan (n = 1-4) display no discernable dipole moment, while C60Yb is strongly polar. This suggests that the fullerene and small alkali clusters fail to form a charge-transfer bond in the helium matrix despite their strong van der Waals attraction. The C60Yb dipole moment, on the other hand, is in agreement with the value expected for an ionic complex.

Shells in CO2 clusters.

Abundance spectra of (CO2)N clusters up to N ≈ 500 acquired under a wide range of adiabatic expansion conditions are analyzed within the evaporative ensemble framework. The analysis reveals that the cluster stability functions display a strikingly universal pattern for all expansion conditions. These patterns reflect the inherent properties of individual clusters. From this analysis the size-dependent cluster binding energies are determined, shell and subshell closing sizes are identified, and cuboctahedral packing ordering for sizes above N ≈ 130 is confirmed. It is demonstrated that a few percent variation in the dissociation energies translates into significant abundance variations, especially for the larger clusters.

Electric deflection of imidazole dimers and trimers in helium nanodroplets: Dipole moments, structure, and fragmentation.

Deuterated imidazole (IM) molecules, dimers, and trimers formed in liquid helium nanodroplets are studied by the electrostatic beam deflection method. Monitoring the deflection profile of (IM)D+ provides a direct way to establish that it is the primary product of the ionization-induced fragmentation both of (IM)2 and (IM)3. The magnitude of the deflection determines the electric dipole moments of the parent clusters: nearly 9 D for the dimer and 14.5 D for the trimer. These very large dipole values confirm theoretical predictions and derive from a polar chain bonding arrangement of the heterocyclic imidazole molecules.

Oriented Polar Molecules Trapped in Cold Helium Nanodropets: Electrostatic Deflection, Size Separation, and Charge Migration.

Helium nanodroplets doped with polar molecules are studied by electrostatic deflection. This broadly applicable method allows even polyatomic molecules to attain subkelvin temperatures and nearly full orientation in the field. The resulting intense force from the field gradient strongly deflects even droplets with tens of thousands of atoms, the most massive neutral systems studied by beam "deflectometry." We use the deflections to extract droplet size distributions. Moreover, since each host droplet deflects according to its mass, spatial filtering of the deflected beam translates into size filtering of neutral fragile nanodroplets. As an example, we measure the dopant ionization probability as a function of droplet radius and determine the mean free path for charge hopping through the helium matrix. The technique will enable separation of doped and neat nanodroplets and size-dependent spectroscopic studies.

Direct detection of polar structure formation in helium nanodroplets by beam deflection measurements.

Long-range intermolecular forces are able to steer polar molecules submerged in superfluid helium nanodroplets into highly polar metastable configurations. We demonstrate that the presence of such special structures can be identified, in a direct and determinative way, by electrostatic deflection of the doped nanodroplet beam. The measurement also establishes the structures' electric dipole moments. In consequence, the introduced approach is complementary to spectroscopic studies of low-temperature molecular assembly reactions. It is enabled by the fact that within the cold superfluid matrix the molecular dipoles become nearly completely oriented by the applied electric field. As a result, the massive (tens of thousands of helium atoms) nanodroplets undergo significant deflections. The method is illustrated here by an application to dimers and trimers of dimethyl sulfoxide (DMSO) molecules. We interpret the experimental results with ab initio theory, mapping the potential energy surface of DMSO complexes and simulating their low temperature aggregation dynamics.