David M. Rayner

Structures of neutral Au7, Au19, and Au20 clusters in the gas phase.

The catalytic properties of gold nanoparticles are determined by their electronic and geometric structures. We revealed the geometries of several small neutral gold clusters in the gas phase by using vibrational spectroscopy between 47 and 220 wavenumbers. A two-dimensional structure for neutral Au7 and a pyramidal structure for neutral Au20 can be unambiguously assigned. The reduction of the symmetry when a corner atom is cut from the tetrahedral Au20 cluster is directly reflected in the vibrational spectrum of Au19.

Polarization-selective etching in femtosecond laser-assisted microfluidic channel fabrication in fused silica.

We fabricate microchannels in fused silica by femtosecond laser irradiation followed by etching in diluted hydrofluoric acid. We show a dramatic dependence of the etch rate on the laser polarization, spanning 2 orders of magnitude. We establish the existence of an energy-per-pulse threshold at which etching of the laser-modified zones becomes highly polarization selective. The enhanced selective etching is due to long-range, periodic, polarization-dependent nanostructures formed in the laser-modified material.

Pulse duration dependence of femtosecond-laser-fabricated nanogratings in fused silica

Femtosecond laser radiation tightly focused in bulk fused silica is used to generate self-ordered nanogratings when the sample is translated under the lens at constant speed. The nanogratings are preserved over a length scale of millimeters. We demonstrate that nanogratings are formed for all pulse durations tested, ranging from 40to500fs, and that the pulse energy threshold for this phenomenon increases with decreasing pulse duration. We use high spatial resolution diagnostics based upon selective chemical etching followed by atomic force microscopy and scanning electron microscopy to reveal the morphology of the nanogratings.

The structure of Nb3O and Nb3O+ determined by pulsed field ionization–zero electron kinetic energy photoelectron spectroscopy and density functional theory

The geometrical structures of the ground states of triniobium monoxide, Nb3O, and its cation, Nb3O+, have been determined by an experimental and theoretical study. Vibrationally resolved photoelectron spectra of an Nb3O cluster beam were obtained at 100 and 300 K using the pulsed field ionization‐zero electron kinetic energy technique. The spectra were simulated by calculating multidimensional Franck–Condon factors using the geometries and harmonic vibrational frequencies obtained from density functional theory for the minimum energy structures of the ion and neutral molecule. The rather remarkable agreement between the experiment and the simulated spectra establishes that Nb3O and Nb3O+ have planar C2v structures with the oxygen atom bridging two niobium atoms. These are the most complex transition metal cluster structures to date to be characterized by gas phase spectroscopic techniques.

Femtosecond laser-induced refractive index modification in multicomponent glasses

We present a comprehensive study on femtosecond laser-induced refractive index modification in a wide variety of multicomponent glasses grouped as borosilicate, aluminum–silicate, and heavy-metal oxide glasses along with lanthanum–borate and sodium–phosphate glasses. By using high-spatial resolution refractive index profiling techniques, we demonstrate that under a wide range of writing conditions the refractive index modification in multicomponent glasses can be positive, negative, or nonuniform, and exhibits a strong dependence on the glass composition. With the exception of some aluminum–silicate glasses all other glasses exhibited a negative/nonuniform index change. We also demonstrate direct writing of waveguides in photosensitive Foturan® glass with a femtosecond laser without initiating crystallization by thermal treatment. Upon ceramization of lithium–aluminum–silicate glasses such as Foturan®, Zerodur®, and Robax® we observe switching of laser-induced refractive index change from being positive t...

Field performance of a laser fluorosensor for the detection of oil spills.

An airborne laser fluorosensor is described that was designed to detect and identify targets by means of the characteristic fluorescence emission spectrum. The first field trials of the sensor over marine oil and dye spills are reported. A correlation technique has been developed that, when applied to the data collected during these field trials, clearly differentiated among dye, the two crude oils, and the general fluorescence background of ocean water.

Ultrashort pulse non-linear optical absorption in transparent media

A focused ultrashort pulse can reach high enough intensity that non-linear ionization dominates its interaction with transparent media while still having relatively low fluence. In this case, the energy extracted from the beam can counter self-focusing by energy depletion and plasma formation, providing controlled energy deposition that can modify the material in a highly local manner. We demonstrate that non-linear absorption limits the intensity that can be reached and that the energy is deposited prior to the focus. We model the energy distribution, and predict and measure the energy transmitted through the focus. We establish the threshold intensity for non-linear ionization in dielectrics at ~ 10(1)(3) W cm-(2). We use the refractive index modification that the non-linear ionization causes in glass to image the spatial distribution of the energy deposition.

OPTICAL ABSORPTION SPECTRA OF AU7, AU9, AU11, AND AU13, AND THEIR CATIONS : GOLD CLUSTERS WITH 6, 7, 8, 9, 10, 11, 12, AND 13 S-ELECTRONS

The optical absorption spectra of a series of small gold clusters and their cations have been measured, between 1.9 and 5.6 eV, using a method based upon the photodepletion of a molecular beam of their van der Waals complexes containing one and two xenon atoms. This method provides size‐specific information even though the molecular beam contains a wide range of cluster sizes. There is little difference between the spectra of complexes containing one or two xenon atoms. However there is a pronounced odd–even alternation in the spectra of gold clusters with differing numbers of valence s electrons. This alternation is described in terms of a simple electron pairing scheme. The spectrum for Au13 is in reasonable agreement with Dirac scattered‐wave molecular orbital considerations for icosahedral Au13 [A. F. Ramos, R. Arratia‐Perez, and G. L. Malli, Phys. Rev. B 35, 3790 (1987)]. This description of the molecular and electronic structure of small gold clusters in terms of localized molecular orbitals is cont...

Size and charge effects on the binding of CO to late transition metal clusters

We report on the size and charge dependence of the C-O stretching frequency, nu(CO), in complexes of CO with gas phase anionic, neutral, and cationic cobalt clusters (Co(n)CO(-0+)), anionic, neutral, and cationic rhodium clusters (Rh(n)CO(-0+)), and cationic nickel clusters (Ni(n)CO(+)) for n up to 37. We develop models, based on the established vibrational spectroscopy of organometallic carbonyl compounds, to understand how cluster size and charge relate to nu(CO) in these complexes. The dominating factor is the available electron density for backdonation from the metal to the CO pi* orbital. Electrostatic effects play a significant but minor role. For the charged clusters, the size trends are related to the dilution of the charge density at the binding site on the cluster as n increases. At large n, nu(CO) approaches asymptotes that are not the same as found for nu(CO) on the single crystal metal surfaces, reflecting differences between binding sites on medium sized clusters and the more highly coordinated metal surface sites.

REACTIVITY OF NIOBIUM CLUSTERS WITH NITROGEN AND DEUTERIUM

Absolute rate coefficients are reported for reactions of Nbn clusters (n=2–20) with D2 and N2 at 280, 300, and 370 K. Most clusters are highly reactive but there are conspicuous exceptions at n=8, 10, and 16 for both D2 and N2. The origin of this trend in reactivity with cluster size and the reason why D2 and N2 show similar trends are discussed. Density functional theory (DFT) electronic structure calculations have been used to investigate the details of the reactions for the smallest clusters Nb2 and Nb8 with H2 and N2. The steric and electronic requirements for dissociation of H2 and N2 are described in terms of frontier orbital interactions. The main conclusion from the DFT calculations is that complete dissociation of H2 or N2 requires charge transfer by transit of an avoided crossing between neutral and ionic potentials. This idea is extended to larger clusters by using a simple charge transfer model that predicts an inverse correlation between reactivity and an appropriately defined effective ioniz...