Versailles Project on Advanced Materials and Standards interlaboratory study on intensity calibration for x-ray photoelectron spectroscopy instruments using low-density polyethylene.

We report the results of a Versailles Project on Advanced Materials and Standards interlaboratory study on the intensity scale calibration of x-ray photoelectron spectrometers using low-density polyethylene (LDPE) as an alternative material to gold, silver, and copper. An improved set of LDPE reference spectra, corrected for different instrument geometries using a quartz-monochromated Al Kα x-ray source, was developed using data provided by participants in this study. Using these new reference spectra, a transmission function was calculated for each dataset that participants provided. When compared to a similar calibration procedure using the NPL reference spectra for gold, the LDPE intensity calibration method achieves an absolute offset of ∼3.0% and a systematic deviation of ±6.5% on average across all participants. For spectra recorded at high pass energies (≥90 eV), values of absolute offset and systematic deviation are ∼5.8% and ±5.7%, respectively, whereas for spectra collected at lower pass energies (<90 eV), values of absolute offset and systematic deviation are ∼4.9% and ±8.8%, respectively; low pass energy spectra perform worse than the global average, in terms of systematic deviations, due to diminished count rates and signal-to-noise ratio. Differences in absolute offset are attributed to the surface roughness of the LDPE induced by sample preparation. We further assess the usability of LDPE as a secondary reference material and comment on its performance in the presence of issues such as variable dark noise, x-ray warm up times, inaccuracy at low count rates, and underlying spectrometer problems. In response to participant feedback and the results of the study, we provide an updated LDPE intensity calibration protocol to address the issues highlighted in the interlaboratory study. We also comment on the lack of implementation of a consistent and traceable intensity calibration method across the community of x-ray photoelectron spectroscopy (XPS) users and, therefore, propose a route to achieving this with the assistance of instrument manufacturers, metrology laboratories, and experts leading to an international standard for XPS intensity scale calibration.

Imaging Intra- and Interparticle Acousto-plasmonic Vibrational Dynamics with Ultrafast Electron Microscopy.

We report real-space, time-resolved imaging of coherently excited acoustic phonon modes in plasmonic nanoparticles via femtosecond electron imaging with an ultrafast electron microscope. The particles studied were cetyl trimethylammonium bromide stabilized Au nanorods (40 × 120 nm), and the particular specimen configurations for which photoinduced vibrational modes were visualized consisted of a single, isolated nanocrystal and a cluster of four irregularly arranged and randomly oriented particles, all supported on an amorphous Si3N4 membrane. In both configurations, we are able to resolve discrete intraparticle acoustic phonon modes via diffraction-contrast modulation with bright-field femtosecond electron imaging. For the single nanorod, we spatiotemporally mapped the intraparticle vibrational energy distribution and decay times. With Fourier filtering, acoustic phonons ranging from 4 to 30 GHz (250 to 33 ps periods, respectively) were visualized, corresponding to bending, extensional, and higher-order modes. Furthermore, heterogeneously distributed intraparticle decay times, ranging from 3 to 10 ns, were spatially mapped, indicating a strong dependence on coupling of the mode to the underlying substrate. For a cluster of four randomly oriented nanorods, we are able to image acoustic phonon modes that are strongly localized to particular particle-particle contact regions within the aggregate. A vibrational mode occurring at 27 GHz (37 ps period) was observed to occur at a 10 nm side-to-end contact region, with other intraparticle points at distances of 20 and 50 nm from the region showing no such dynamics, although the initial few-picosecond diffraction-contrast response was observed changing sign in moving from the end to the center of the particle. Excellent agreement is found between the spatiotemporally mapped vibrational-mode symmetries and finite-element simulations of supported modes in a polymer-coated Au nanorod supported on a Si3N4 membrane. This experiment resolves both the structure and dynamic properties of the plasmonic assembly, providing insight into the characteristics of complex plasmonic assemblies that ultimately determine their response to ultrafast excitation.

Reactive and unreactive pathways in a photochemical ring opening reaction from 2D femtosecond stimulated Raman.

Two-dimensional femtosecond stimulated Raman spectroscopy (2D-FSRS) is used to probe the structural evolution of a modified cyclohexadiene as it undergoes a photoinduced ring opening reaction. Analysis of the excited state stimulated Raman vibrational data reveals oscillations of the center frequencies and amplitudes of 21 high frequency modes. These oscillations in vibrational properties are due to anharmonic couplings between the high frequency finger print modes and the impulsively driven low frequency molecular distortions in the excited state. The largest anharmonic couplings, with intrinsic oscillation magnitudes of up to 40 cm(-1), are observed between the 467 cm(-1) C-C bend and the 1333 cm(-1) C-C stretch with the 191 cm(-1) methyl wag, all of which are centered on the reactive cyclohexadiene moiety. Conversely, motions located on the periphery - the 993 cm(-1) phenyl bend, the 1389 cm(-1) methyl bend and 1580 cm(-1) phenyl C-C stretch - are coupled with the 104 cm(-1) asymmetric bend. These couplings reveal two key energetic pathways: one leading to formation of the ring-opened product and the other reversion back to the ground state. This work is also important because it presents a new powerful method for measuring anharmonicities of potential energy surfaces and determining their role in chemical reactivity.

Optimally shaped narrowband picosecond pulses for femtosecond stimulated Raman spectroscopy.

A comparison between a Fabry-Pérot etalon filter and a conventional grating filter for producing the picosecond (ps) Raman pump pulses for femtosecond stimulated Raman spectroscopy (FSRS) is presented. It is shown that for pulses of equal energy the etalon filter produces Raman signals twice as large as that of the grating filter while suppressing the electronically resonant background signal. The time asymmetric profile of the etalon-generated pulse is shown to be responsible for both of these observations. A theoretical discussion is presented which quantitatively supports this hypothesis. It is concluded that etalons are the ideal method for the generation of narrowband ps pulses for FSRS because of the optical simplicity, efficiency, improved FSRS intensity and reduced backgrounds.

Steric hindrance of photoswitching in self-assembled monolayers of azobenzene and alkane thiols.

Surface-bound azobenzenes exhibit reversible photoswitching via trans-cis photoisomerization and have been proposed for a variety of applications such as photowritable optical media, liquid crystal displays, molecular electronics, and smart wetting surfaces. We report a novel synthetic route using simple protection chemistry to form azobenzene-functionalized SAMs on gold and present a mechanistic study of the molecular order, orientation, and conformation in these self-assembled monolayers (SAMs). We use vibrational sum-frequency generation (VSFG) to characterize their vibrational modes, molecular orientation, and photoisomerization kinetics. Trans-cis conformational change of azobenzene leads to the change in the orientation of the nitrile marker group detected by VSFG. Mixed SAMs of azobenzene and alkane thiols are used to investigate the steric hindrance effects. While 100% azobenzene SAMs do not exhibit photoisomerization due to tight packing, we observe reversible switching (>10 cycles) in mixed SAMs with only 34% and 50% of alkane thiol spacers.

Plasmon resonant enhancement of carbon monoxide catalysis.

Irradiating gold nanoparticles at their plasmon resonance frequency creates immense plasmonic charge and high temperatures, which can be used to drive catalytic reactions. By integrating strongly plasmonic nanoparticles with strongly catalytic metal oxides, significant enhancements in the catalytic activity can be achieved. Here, we study the plasmonically driven catalytic conversion of CO to CO(2) by irradiating Au nanoparticle/Fe(2)O(3) composites. The reaction rate of this composite greatly exceeds that of the Au nanoparticles or Fe(2)O(3) alone, indicating that this reaction is not driven solely by the thermal (plasmonic) heating of the gold nanoparticles but relies intimately on the interaction of these two materials. A comparison of the plasmonically driven catalytic reaction rate with that obtained under uniform heating shows an enhancement of at least 2 orders of magnitude.

Optical manipulation of plasmonic nanoparticles, bubble formation and patterning of SERS aggregates.

We present an optical method for patterning SERS (surface-enhanced Raman spectroscopy)--enhancing aggregates of gold nanoparticles, using a focused laser beam to optically trap the nanoparticles in suspension. At high laser powers, heat generated from the plasmonic excitation causes boiling of the aqueous suspension and the formation of gaseous bubbles of water vapor. By measuring the Raman peak of the hydroxyl bond of water, the temperature in the laser spot during the aggregation can be determined in situ. The hydrophilic nanoparticles are found to aggregate at the liquid-vapor interface. By allowing the suspension to dry, a ring of gold nanoparticles is deposited on the substrate, producing a highly SERS-active region. These aggregates are studied using optical microscopy, scanning electron microscopy and micro-Raman spectroscopy.

The quasi-one-dimensional colloid fluid revisited.

We report the results of studies of the pair correlation function and equation of state of a quasi-one-dimensional colloid suspension, focusing attention on the behavior in the density range near close packing. Our data show that, despite deviations from true one-dimensional geometry, the colloid fluid is well described as a hard rod Tonks fluid. In our experimental realization, the colloid suspension does not wet the confining walls, one consequence of which is a surface tension induced weak attractive interaction between the particles. The reality of this interaction is confirmed after correction of the raw experimental data for overlap of the optical images of particles that are nearly in contact and by an alternative particle location algorithm based on edge location.

Pair diffusion in quasi-one- and quasi-two-dimensional binary colloid suspensions.

The authors report the results of measurements of the center of mass and relative pair diffusion coefficients in quasi-one-dimensional (q1D) and quasi-two-dimensional (q2D) binary colloid suspensions. The new results extend the findings of similar studies of one-component quasi-one-dimensional and quasi-two-dimensional colloid suspensions. Our principal new finding is that the presence of the smaller diameter component can destroy the oscillatory structure of the separation dependence of the q2D relative pair diffusion coefficient of the large particles even though the oscillatory character of the large particle equilibrium pair correlation function remains prominent, and that no such effect occurs with the q1D suspension. An interpretation of these results is proposed.