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The cyclic water hexamer, a higher energy isomer than the cage structure previously characterized in the gas phase, was formed in liquid helium droplets and studied with infrared spectroscopy. This isomer is formed selectively as a result of unique cluster growth processes in liquid helium. The experimental results indicate that the cyclic hexamer is formed by insertion of water molecules into smaller preformed cyclic complexes and that the rapid quenching provided by the liquid helium inhibits its rearrangement to the more stable cage structure.

The technique of single-particle mass spectrometry has been coupled to a reaction flow tube to measure the uptake coefficient, γ, of ozone (O 3 ) by oleic acid (9-octadecenoic acid) aerosol particles. The reaction was followed by monitoring the decrease of oleic acid in the size-selected particles as a function of O 3 exposure. The reactive uptake coefficient is found to depend on the size of the particle, with γ meas ranging from (7.3 ( 1.5) × 10 -3 to (0.99 ( 0.09) × 10 -3 for particles ranging in radius from 680 nm to 2.45 µm. It is suggested that the decrease in γ meas with increasing particle size results from the reaction being limited by the diffusion of oleic acid within the particle, and based on our measurements we estimate the value of γ to be (5.8-9.8) × 10 -3 for particles that are not limited by oleic acid diffusion. A reaction model that includes simultaneous diffusion and reaction of both O 3 and oleic acid is developed and used to fit the observed rates of reaction. Solutions obtained from this model indicate that oleic acid must diffuse within the particle more slowly than is predicted by the measured oleic acid self-diffusion constant. 1 It is proposed that this oleic acid-diffusionlimited uptake is attributable to the ozonolysis reaction products. Furthermore, these experiments demonstrate that it is not always possible to describe heterogeneous uptake by a model that decouples all relevant processes, including reaction and diffusion. Finally, the possible implications that these findings have for the role of particle morphology in the reaction of gas-phase species with atmospheric aerosols are discussed.

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It is shown that in the low-temperature (0.37 kelvin) environment of superfluid helium droplets, long-range dipole-dipole forces acting between two polar molecules can result in the self-assembly of noncovalently bonded linear chains. At this temperature the effective range of these forces is on the nanometer scale, making them important in the growth of nanoscale structures. In particular, the self-assembly of exclusively linear hydrogen cyanide chains is observed, even when the folded structures are energetically favored. This suggests a design strategy for the growth of new nanoscale oligomers composed of monomers with defined dipole (or higher order) moment directions.

High-resolution near-infrared spectra are reported for all of the O–H stretch vibrational bands of the water dimer. The four O–H vibrations are characterized as essentially independent proton-donor or proton-acceptor motions. In addition to the rotational and vibrational information contained in these spectra, details are obtained concerning the internal tunneling dynamics in both the ground and excited vibrational states. These results show that for tunneling motions which involve the interchange of the proton donor and acceptor molecules, the associated frequencies decrease substantially due to vibrational excitation. The predissociation lifetimes for the various states of the dimer are determined from linewidth measurements. These results clearly show that the predissociation dynamics is strongly dependent on the tunneling states, as well as the Ka quantum number, indicating that the internal tunneling dynamics plays an important role in determining the dissociation rate in this complex.

Infrared laser spectroscopy is used to study the four lowest energy tautomers of guanine, isolated in helium nanodroplets. The large number of vibrational bands observed in the infrared spectrum are assigned by comparing the corresponding experimental vibrational transition moment angles with those obtained from ab initio theory. The result is the conclusive assignment of the spectrum to the N9H-Keto, N7H-Keto, N9Ha-Enol(trans), and N9Hb-Enol(cis) tautomers. The dipole moments of these tautomers are also experimentally determined and compared with ab initio theory.

Small van der Waals clusters of sulfur hexafluoride (SF6) and mixed SF6-rare gas clusters were prepared inside large droplets of helium-4, with each droplet consisting of about 4000 helium atoms. A diode laser was used to measure the high-resolution infrared spectra of these clusters in the vicinity of the nu3 vibrational mode. In all cases rotational structure was observed, indicating that the embedded species rotate nearly freely, although they had been cooled to a temperature of 0.37 kelvin. The results indicate that helium droplets are probably superfluid and thereby provide a uniquely cold yet gentle matrix for high-resolution spectroscopy.