The structure of ions in water at a hydrophobic interface influences important processes throughout chemistry and biology. However, experiments to measure these structures are limited by the distribution of configurations present and the inability to selectively probe the interfacial region. Here, protonated nanoclusters containing benzene and water are produced in the gas phase, size-selected, and investigated with infrared laser spectroscopy. Proton stretch, free OH, and hydrogen-bonding vibrations uniquely define protonation sites and hydrogen-bonding networks. The structures consist of protonated water clusters binding to the hydrophobic interface of neutral benzene via one or more π-hydrogen bonds. Comparison to the spectra of isolated hydronium, zundel, or eigen ions reveals the inductive effects and local ordering induced by the interface. The structures and interactions revealed here represent key features expected for aqueous hydrophobic interfaces.

Singly and doubly charged chromium-water ion-molecule complexes are produced by laser vaporization in a pulsed-nozzle cluster source. These species are detected and mass-selected in a specially designed time-of-flight mass spectrometer. Vibrational spectroscopy is measured for these complexes in the O-H stretching region using infrared photodissociation spectroscopy and the method of rare gas atom predissociation. Infrared excitation is not able to break the ion-water bonds in these systems, but it leads to elimination of argon, providing an efficient mechanism for detecting the spectrum. The O-H stretches for both singly and doubly charged complexes are shifted to frequencies lower than those for the free water molecule, and the intensity of the symmetric stretch band is strongly enhanced relative to the asymmetric stretch. Partially resolved rotational structure for both complexes shows that the H-O-H bond angle is greater than it is in the free water molecule. These polarization-induced effects are enhanced in the doubly charged ion relative to its singly charged analog.

Singly and doubly charged manganese-water cations, and their mixed complexes with attached argon atoms, are produced by laser vaporization in a pulsed nozzle source. Complexes of the form Mn(+)(H(2)O)Ar(n) (n = 1-4) and Mn(2+)(H(2)O)Ar(4) are studied via mass-selected infrared photodissociation spectroscopy, detected in the mass channels corresponding to the elimination of argon. Sharp resonances are detected for all complexes in the region of the symmetric and asymmetric stretch vibrations of water. With the guidance of density functional theory computations, specific vibrational band resonances are assigned to complexes having different argon attachment configurations. In the small singly charged complexes, argon adds first to the metal ion site and later in larger clusters to the hydrogens of water. The doubly charged complex has argon only on the metal ion. Vibrations in all of these complexes are shifted to lower frequencies than those of the free water molecule. These shifts are greater when argon is attached to hydrogen and also greater for the dication compared to the singly charged species. Cation binding also causes the IR intensities for water vibrations to be much greater than those of the free water molecule, and the relative intensities are greater for the symmetric stretch than the asymmetric stretch. This latter effect is also enhanced for the dication complex.

Singly and doubly charged scandium-water ion-molecule complexes are produced in a supersonic molecular beam by laser vaporization. These ions are mass analyzed and size selected in a specially designed reflectron time-of-flight spectrometer. To probe their structure, vibrational spectroscopy is measured for these complexes in the O-H stretching region using infrared laser photodissociation and the method of rare gas atom predissociation, also known as "tagging." The O-H stretches in these systems are shifted to lower frequency than those for the free water molecule, and the intensity of the symmetric stretch band is strongly enhanced relative to the asymmetric stretch. These effects are more prominent for the doubly charged ions. Partially resolved rotational structure for the Sc(+)(H(2)O)Ar complex shows that the H-O-H bond angle is larger than it is in the free water molecule. Fragmentation and spectral patterns indicate that the coordination of the Sc(2+) ion is filled with six ligands (one water and five argons).

Mesoporous thin films of TiO 2 doped with silver can undergo spectacular microstructural modifications upon laser scanning at visible wavelengths through the excitation of a localized surface plasmon resonance in Ag nanoparticles (NPs). The latter can result in competitive physicochemical mechanisms, leading either to the shrinkage or to the growth of NPs depending on the exposure conditions. Contrary to intuition, we provide evidence that the speed of the laser scan controls the size of NPs as follows: low speeds lead to silver oxidation and a decrease in the NP size, whereas high speeds induce rapid temperature rises and a spectacular growth of NPs. Both regimes are separated by a speed threshold that depends on extrinsic and intrinsic parameters such as laser power, beam diameter, and initial size of Ag NPs. We propose here a comprehensive model based on a set of coupled differential equations describing the transformations of silver under laser excitation between the Ag 0 , Ag + , and metallic NP states, which provides a convincing physicochemical explanation of the experimental findings. This study constitutes a significant advance in the understanding of oxidation−reduction processes involved during laser exposure of metallic NPs and opens new directions to control their growth rate and their final size.

The hydrogen abstraction/acetylene addition (HACA) mechanism has long been viewed as a key route to aromatic ring growth of polycyclic aromatic hydrocarbons (PAHs) in combustion systems. However, doubt has been drawn on the ubiquity of the mechanism by recent electronic structure calculations which predict that the HACA mechanism starting from the naphthyl radical preferentially forms acenaphthylene, thereby blocking cyclization to a third six-membered ring. Here, by probing the products formed in the reaction of 1- and 2-naphthyl radicals in excess acetylene under combustion-like conditions with the help of photoionization mass spectrometry, we provide experimental evidence that this reaction produces 1- and 2-ethynylnaphthalenes (C12 H8 ), acenaphthylene (C12 H8 ) and diethynylnaphthalenes (C14 H8 ). Importantly, neither phenanthrene nor anthracene (C14 H10 ) was found, which indicates that the HACA mechanism does not lead to cyclization of the third aromatic ring as expected but rather undergoes ethynyl substitution reactions instead.

Singly charged zinc-water cations are produced in a pulsed supersonic expansion source using laser vaporization. Zn(+)(H2O)n (n = 1-4) complexes are mass selected and studied with infrared laser photodissociation spectroscopy, employing the method of argon tagging. Density functional theory (DFT) computations are used to obtain the structures and vibrational frequencies of these complexes and their isomers. Spectra in the O-H stretching region show sharp bands corresponding to the symmetric and asymmetric stretches, whose frequencies are lower than those in the isolated water molecule. Zn(+)(H2O)nAr complexes with n = 1-3 have O-H stretches only in the higher frequency region, indicating direct coordination to the metal. The Zn(+)(H2O)2-4Ar complexes have multiple bands here, indicating the presence of multiple low energy isomers differing in the attachment position of argon. The Zn(+)(H2O)4Ar cluster uniquely exhibits a broad band in the hydrogen bonded stretch region, indicating the presence of a second sphere water molecule. The coordination of the Zn(+)(H2O)n complexes is therefore completed with three water molecules.

The structure of the phenylacetylene-water complex has been elucidated based on spectral shifts in electronic and vibrational transitions. Phenylacetylene forms a cyclic complex with water incorporating C-H...O and O-H...pi hydrogen bonds, which is different from both the benzene-water and acetylene-water complexes, even though phenylacetylene combines the features of both benzene and acetylene. Formation of such a complex can be rationalized on the basis of cooperativity between the two sets of hydrogen bonds.