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The modification of polymer surfaces using laser light is important for many applications in the nano‐, bio‐ and chemical sciences. Such capabilities have supported advances in biomedical devices, electronics, information storage, microfluidics, and other applications. In most cases, these modifications require high power lasers that are expensive and require specialized equipment and facilities to minimize risk of hazardous radiation. Additionally, polymer systems that can be easily modified by lasers are often complex and costly to prepare. In this report, these challenges are addressed with the discovery of low‐cost sulfur copolymers that can be rapidly modified with lasers emitting low‐power infrared and visible light. The featured copolymers are made from elemental sulfur and either cyclopentadiene or dicyclopentadiene. Using a suite of lasers with discreet wavelengths (532, 638 and 786 nm) and powers, a variety of surface modifications could be made on the polymers such as controlled swelling or etching via ablation. The facile synthesis and laser modification of these polymer systems were exploited in applications such as direct laser lithography and erasable information storage. [ABSTRACT FROM AUTHOR]

The modification of polymer surfaces using laser light is important for many applications in the nano‐, bio‐ and chemical sciences. Such capabilities have supported advances in biomedical devices, electronics, information storage, microfluidics, and other applications. In most cases, these modifications require high power lasers that are expensive and require specialized equipment and facilities to minimize risk of hazardous radiation. Additionally, polymer systems that can be easily modified by lasers are often complex and costly to prepare. In this report, these challenges are addressed with the discovery of low‐cost sulfur copolymers that can be rapidly modified with lasers emitting low‐power infrared and visible light. The featured copolymers are made from elemental sulfur and either cyclopentadiene or dicyclopentadiene. Using a suite of lasers with discreet wavelengths (532, 638 and 786 nm) and powers, a variety of surface modifications could be made on the polymers such as controlled swelling or etching via ablation. The facile synthesis and laser modification of these polymer systems were exploited in applications such as direct laser lithography and erasable information storage. [ABSTRACT FROM AUTHOR]

The torsional constant (F) is a parameter extracted from spectroscopic analyses of molecules possessing a methyl group. Its value depends primarily on the methyl structure. Widely varying F values have been reported for substituted toluenes in their ground electronic state, first excited singlet electronic state or the ground electronic state of the cation. Conventionally, this variability is assumed to indicate significant changes in the methyl structure with substituent, its position on the ring and the electronic state. However, when the large amplitude methyl torsion interacts with other, small amplitude vibrations, this interpretation is misleading as the torsional states are shifted to lower energy, resulting in a reduced, 'effective' F being determined. We have observed coupling between methyl torsion and the low frequency, methyl group out-of-plane wag vibration in toluene, p-fluorotoluene, m-fluorotoluene and N-methylpyrrole, leading us to postulate that, since such motion will be present whenever the methyl group is attached to a planar frame, this type of interaction is widespread. This is tested for a series of substituted toluenes by comparing the methyl group structure calculated by quantum chemistry with the experimental torsional constants. The quantum chemistry calculations predict little variation in the methyl structure across a wide range of substituents, ring positions and electronic state. The wide variation in F values observed in experimental analyses is attributed to the torsion-vibration interaction affecting the torsional band structure, so that measured F values become 'effective constants'. Comparisons between calculated and experimental torsional constants need to be cognisant of this effect. [ABSTRACT FROM AUTHOR]

Observations of the torsional and low-lying vibrational–torsional states of toluene, p-fluorotoluene, and m-fluorotoluene using the technique of two dimensional laser induced fluorescence (2D-LIF) have revealed interactions between the methyl torsion and low frequency out-of-plane methyl wagging vibration. These interactions can change the values of constants extracted from the analysis of rotational spectra, which usually assume that the large amplitude torsional motion can be treated independent of the small amplitude vibrations. Since out-of-plane methyl wagging modes will be present whenever a methyl group is attached to a planar frame, this type of torsion–vibration interaction is potentially widespread; it is thus important to establish the extent and strength of this type of interaction. 2D-LIF is limited to molecules that fluoresce from excited electronic states, and to explore interactions between torsion and methyl wagging vibrations in a wide range of molecules necessitates developing alternative experimental approaches. Infrared absorption spectroscopy is one such approach. It is shown that for the low torsional barrier case, the torsional sequence bands accompanying the out-of-plane methyl wagging transition provide a sensitive probe of the interaction. As an illustration, the far infrared absorption spectrum of toluene in the region of the M20 band (∼205 cm−1) is presented and analyzed. The torsional sequence structure provides insight into the higher torsional states (up to m = 7) in the ground vibrational state and M20. An analysis of these bands enables the torsion–vibration coupling and torsional constants to be extracted. A general method to analyze such spectra is presented. [ABSTRACT FROM AUTHOR]

With increasing use of infrared imaging in medical diagnostics, military and civilian surveillance, and navigation of autonomous vehicles, there is a need for low‐cost alternatives to traditional materials used in infrared optics such as germanium. Sulfur‐rich copolymers hold promise, as they are made from low‐cost feedstocks and have a high refractive index. In this report, cyclopentadiene is copolymerized with sulfur to provide a plastic with the highest long‐wave infrared transparency reported to date for this class of materials. Diverse lens architectures are accessible through melt casting or reactive injection molding. The featured copolymer is black, which enabled its use as an infrared‐transparent blind for protection of thermal imaging equipment and clandestine surveillance. These findings portend expanded use of sulfur copolymers in infrared optics. [ABSTRACT FROM AUTHOR]

We report results of a two dimensional laser induced fluorescence study of torsional states, low frequency vibrations, and combinations of torsion with low frequency vibration in m-fluorotoluene up to 560 cm−1 in S0 and 350 cm−1 in S1. Evidence is presented for interactions between torsion and low frequency vibrations in both S0 and S1, demonstrating that the coupling of torsion and vibration observed previously in toluene and p-fluorotoluene extends to a molecule with a threefold torsional barrier. This barrier is low in S0 (20 cm−1) and modest in S1 (116 cm−1). The methyl torsion-vibration interaction is much larger for the mode involving out-of-plane wagging of the methyl group with respect to the planar frame compared with the analogous out-of-plane fluorine atom motion. Methyl group out-of-plane modes were found to be most important for torsion-vibration interactions in toluene and p-fluorotoluene, and the evidence is accumulating that this motion is fundamental in torsion-vibration interactions. Fits of the experimental band positions yield torsion-vibration coupling constants, torsional potential terms (V3 and V6), and rotational constants (F) for the methyl torsion in S0 and S1. The inclusion of torsion-vibration coupling primarily affects V6 and F: |V6| is reduced and F increased, as was seen previously for the G12 molecules, toluene and p-fluorotoluene. The torsional barrier height does not appear to influence the magnitude of the torsion-vibration interaction: the coupling constants for the out-of-plane CH3 wag mode are almost the same in S0 and S1 (15.5 cm−1 and 14.0 cm−1, respectively). [ABSTRACT FROM AUTHOR]

We report two dimensional laser induced fluorescence spectral images exploring the lower torsion-vibration manifolds in S0 (E < 560 cm−1) and S1 (E < 420 cm−1) p-fluorotoluene. Analysis of the images reveals strong torsion-vibration interactions and provides an extensive set of torsion-vibration state energies in both electronic states (estimated uncertainty ±0.2 cm−1), which are fit to determine key constants including barrier heights, torsional constants, and torsion-vibration interaction constants. The dominant interactions in both electronic states are between methyl torsion (internal rotation) and the lowest frequency out-of-plane modes, D20 and D19, both of which involve a methyl wagging motion. This is the second aromatic (following toluene) for which a significant interaction between torsion and methyl out-of-plane wagging vibrations has been quantified. Given the generic nature of this motion in substituted toluenes and similar molecules, this mechanism for torsion-vibration coupling may be common in these types of molecules. The inclusion of torsion-vibration coupling affects key molecular constants such as barrier heights and torsional (and rotational) constants, and the possibility of such an interaction should thus be considered in spectral analyses when determining parameters in these types of molecules. p-Fluorotoluene is the first molecule in which the role of methyl torsion in promoting intramolecular vibrational energy redistribution (IVR) was established and the observed torsion-vibration coupling provides one conduit for the state mixing that is a precursor to IVR, as originally proposed by Moss et al. [J. Chem. Phys. 86, 51 (1987)]. [ABSTRACT FROM AUTHOR]

This pilot study investigates the formation of aggregates within a desalination plant, before and after pre-treatment, as well as their potential impact on fouling. The objective is to provide an understanding of the biofouling potential of the feed water within a seawater reverse osmosis (SWRO) desalination plant, due to the limited removal of fouling precursors. The 16S and 18S rRNA was extracted from the water samples, and the aggregates and sequenced. Pre-treatment systems, within the plant remove < 5 µm precursors and organisms; however, smaller size particles progress through the plant, allowing for the formation of aggregates. These become hot spots for microbes, due to their nutrient gradients, facilitating the formation of niche environments, supporting the proliferation of those organisms. Aggregate-associated organisms are consistent with those identified on fouled SWRO membranes. This study examines, for the first time, the factors supporting the formation of aggregates within a desalination system, as well as their microbial communities and biofouling potential. [ABSTRACT FROM AUTHOR]

The extraction of electron–liquid phase cross-sections (surface and bulk) is proposed through the measurement of (differential) energy loss spectra for electrons scattered from a liquid micro-jet. The signature physical elements of the scattering processes on the energy loss spectra are highlighted using a Monte Carlo simulation technique, originally developed for simulating electron transport in liquids. Machine learning techniques are applied to the simulated electron energy loss spectra, to invert the data and extract the cross-sections. The extraction of the elastic cross-section for neon was determined within 9% accuracy over the energy range 1–100 eV. The extension toward the simultaneous determination of elastic and ionisation cross-sections resulted in a decrease in accuracy, now to within 18% accuracy for elastic scattering and 1% for ionisation. Additional methods are explored to enhance the accuracy of the simultaneous extraction of liquid phase cross-sections. [ABSTRACT FROM AUTHOR]

Single pulse, solid-state 29Si nuclear magnetic resonance (NMR) spectroscopy offers an additional method of characterisation of opal-A and opal-CT through spin-lattice (T1) relaxometry. Opal T1 relaxation is characterised by stretched exponential (Weibull) function represented by scale (speed of relaxation) and shape (form of the curve) parameters. Relaxation is at least an order of magnitude faster than for silica glass and quartz, with Q3 (silanol) usually faster than Q4 (fully substituted silicates). 95% relaxation (Q4) is achieved for some Australian seam opals after 50 s though other samples of opal-AG may take 4000 s, while some figures for opal-AN are over 10,000 s. Enhancement is probably mostly due to the presence of water/silanol though the presence of paramagnetic metal ions and molecular motion may also contribute. Shape factors for opal-AG (0.5) and opal-AN (0.7) are significantly different, consistent with varying water and silanol environments, possibly reflecting differences in formation conditions. Opal-CT samples show a trend of shape factors from 0.45 to 0.75 correlated to relaxation rate. Peak position, scale and shape parameter, and Q3 to Q4 ratios offer further differentiating feature to separate opal-AG and opal-AN from other forms of opaline silica. T1 relaxation measurement may have a role for provenance verification. In addition, definitively determined Q3/Q4 ratios are in the range 0.1 to 0.4 for opal-AG but considerably lower for opal-AN and opal-CT. [ABSTRACT FROM AUTHOR]

The velocity map imaging technique was used in the investigation of gold(I) butadiynylide, AuC4H-, with images recorded at two excitation wavelengths. The resultant photodetachment spectra show a well defined vibrational progression in the neutral with an energy spacing of 343 ± 3 cm-1. The adiabatic electron affinity was determined to be 1.775 ± 0.005 eV and assigned to the X¹Σ+ X²Σ+ transition between the anionic and neutral ground states. Franck-Condon simulations performed on density functional theory optimized geometries assisted the assignment of linear geometries to the neutral and anion and the observed vibrational progression to that of the Au-C4H stretch. [ABSTRACT FROM AUTHOR]

We report a two dimensional, laser induced fluorescence study of the lowest 345 cm-1 region of S0 toluene. Methyl rotor levels of 00 up to m = 6 and of 201 up to m = 4 are observed. The rotor levels of 00 and 201 have quite different energy spacings that are well fit by a model that includes strong torsion-vibration coupling between them. The model requires that the rotor barrier height be revised from -4.84 cm-1 (methyl hydrogens in a staggered conformation) to +1.57 cm-1 (eclipsed conformation). However, the 3a2'' state lies below the 3aa'' state as expected for a staggered conformation due to energy shifts associated with the torsion-vibration coupling. It is shown that the rotor wave-functions exhibit little localization at the torsional energy minima. The variation in the m = 0 wavefunction probability distribution with torsional angle is shown to be very similar for the previously accepted negative V6 value and the torsion-vibration coupling model as this coupling shifts the phase of the wavefunction by 30° compared with its phase for V6 alone. The presence of a strong ΔƲ = ±1 torsion-vibration coupling involving the lowest frequency vibrational mode provides a potential pathway for rapid intramolecular vibrational energy redistribution at higher energies. [ABSTRACT FROM AUTHOR]

Franck-Condon forbidden transitions involving methyl rotor modes are seen in the S1 ←S0 spectrum of toluene and toluene-like molecules. The strongest of these rotor transitions (m" = 1→m' = 2, m" = 0→m' = 3a1 ", and m" = 1→m' = 4) have been shown by Walker et al. [J. Chem. Phys. 102, 8718 (1995)] to gain intensity through the rotor equivalent of the Herzberg-Teller mechanism. Despite the m" = 0→m' = 3a2 " transition being forbidden in this formalism, it is sporadically observed. We show that this transition derives oscillator strength from incomplete mixing of the -3 and +3 free rotor basis states due to torsion-rotation coupling. Calculations demonstrate that this mechanism quantitatively explains the intensities observed for toluene, including their temperature dependence. Because the -3/+3 mixing is weakest when the torsional barrier height, V6, is small, the m" = 0→m' = 3a2 " transition increases in intensity as ∣V6∣ decreases. The temperature and ∣V6∣ dependencies explain why reports of the 0→3a2 " transition have been intermittent. The torsionrotation coupling mechanism is predicted to also give significant intensity to m = 0→m = 6a2 ' transitions relative to m = 0→m = 6a1 ' transitions and to provide intensity to 0→3a2 transitions in molecules with a 3-fold (V3) barrier. Comparison between the observed and calculated rotor band contours shows, unexpectedly, that the 3a1 " constants fail to predict the 3a2 " contour despite these two states being derived from the same free rotor basis states. Comparison with the observed spectrum also reveals differences in the separation of the S1 3a2 " and 3a1 " levels. The V6 value determined from analysis of the high resolution, rotationally resolved m" = 0→m' = 3a1 " spectrum overestimates the 3a2 "-3a1 " separation by 0.6 cm-1. We postulate that this may be due to torsionvibration coupling. The observed toluene torsion-rotation contours have been modeled to provide estimates of the rotational constants for several of the torsional states. [ABSTRACT FROM AUTHOR]

The methyl rotor and van der Waals vibrational levels in the S1 and S0 states of toluene-Ar have been investigated by the technique of two-dimensional laser induced fluorescence (2D-LIF). The S0 van der Waals and methyl rotor levels are reported for the first time, while improved S1 values are presented. The correlations seen in the 2D-LIF images between the S0 and S1 states lead to a reassignment of key features in the S1 ← S0 excitation spectrum. This reassignment reveals that there are significant changes in the methyl rotor levels in the complex compared with those in bare toluene, particularly at low m. The observed rotor energies are explained by the introduction of a three-fold, V3, term in the torsion potential (this term is zero in toluene) and a reduction in the height of the six-fold, V6, barriers in S0 and S1 from their values in bare toluene. The V3 term is larger in magnitude than the V6 term in both S0 and S1. The constants determined are |V3(S1)| = 33.4 ± 1.0 cm-1, |V3(S0)| = 20.0 ± 1.0 cm-1, V6(S1) = -10.7 ± 1.0 cm-1, and V6(S0) = -1.7 ± 1.0 cm-1. The methyl rotor is also found to couple with van der Waals vibration; specifically, the m″ = 2 rotor state couples with the combination level involving one quantum of the long axis bend and m″ = 1. The coupling constant is determined to be 1.9 cm-1, which is small compared with the values typically reported for torsion-vibration coupling involving ring modes. [ABSTRACT FROM AUTHOR]

Featured Application: Transparent electrodes are critical in many applications. This work probes an approach to make highly conducting, highly transparent electrodes using carbon nanotubes. The morphology of carbon nanotube (CNT) films is an important factor in the performance of CNT/silicon (CNT/Si) heterojunction solar devices. Films have generally been prepared via vacuum filtration from aqueous suspensions. Whilst this enables strong films to be formed quickly, they are highly disordered on the micron scale, with many charge traps and gaps forming in the films. It has been previously established that lowering the filtration speed enables more ordered films to be formed. The use of slow gravity filtration to improve the morphology of CNT films used in the CNT/Si device is reported here. It was found that slow filtration causes significant macroscale inhomogeneity in the CNT films, with concentrated thick regions, surrounded by larger thinner areas. By using atomic force microscopy (AFM), scanning electron microscopy (SEM), and polarised Raman spectroscopy, it was determined that there was no large improvement in directional organisation of the CNTs on the microscale. However, the films were found to be much smoother on the microscale, with arithmetic and root mean square average height deviation values roughly 3 times lower for slow-filtered films compared to fast-filtered films. A comparison was performed with CNT-Si solar cells fabricated with both slow and fast-filtered single-walled CNTs (SWCNT) films. It was found that slow filtration can produce similar photovoltaic results with thinner films. The results demonstrate that film morphology, even without improved CNT alignment, can lead to significant improvement in device performance in some applications. However, slow filtration did not form films of uniform light transmittance over an extended area, causing an increase in the variation in performance between individual devices compared to fast-filtered films. [ABSTRACT FROM AUTHOR]

Inverse vulcanization provides dynamic and responsive materials made from elemental sulfur and unsaturated cross‐linkers. These polymers have been used in a variety of applications such as energy storage, infrared optics, repairable materials, environmental remediation, and precision fertilizers. In spite of these advances, there is a need for methods to recycle and reprocess these polymers. In this study, polymers prepared by inverse vulcanization are shown to undergo reactive compression molding. In this process, the reactive interfaces of sulfur polymers are brought into contact by mechanical compression. Upon heating these molds at relatively low temperatures (≈100 °C), chemical bonding occurs at the polymer interfaces by S−S metathesis. This method of processing is distinct from previous studies on inverse vulcanization because the polymers examined in this study do not form a liquid phase when heated. Neither compression nor heating alone was sufficient to mold these polymers into new architectures, so this is a new concept in the manipulation of sulfur polymers. Additionally, high‐level ab initio calculations revealed that the weakest S−S bond in organic polysulfides decreases linearly in strength from a sulfur rank of 2 to 4, but then remains constant at about 100 kJ mol−1 for higher sulfur rank. This is critical information in engineering these polymers for S−S metathesis. Guided by this insight, polymer repair, recycling, and repurposing into new composites was demonstrated. [ABSTRACT FROM AUTHOR]

For molecules containing a methyl group, high precision fits of rotational line data (microwave spectra) that encompass several torsional states require considerably more constants than are required in comparable rigid molecules. Many of these additional terms are 'torsion-rotation interaction' terms, but their precise physical meaning is unclear. In this paper, we explore the physical origins of many of these additional terms in the case where the methyl group is attached to a planar frame. We show that torsion-vibration coupling, which has been observed in toluene and several substituted toluenes, provides the dominant contribution to a number of the torsion-rotation constants in toluene. It is further demonstrated that this coupling is intimately related to precession of the methyl group. A number of the constants required in the high resolution fits of rotational line data are shown to arise as a natural consequence of methyl precession. By considering several molecules whose rotational line spectra have been fit to high precision, we demonstrate that the experimental evidence is consistent with the occurrence of methyl group precession. Quantum chemistry calculations of the optimised molecular structures at key torsional angles provide further evidence that methyl precession occurs. There is both a torsional angle dependent tilt of the C methyl -frame bond and of the methyl group principal rotation axis relative to the C methyl -frame bond. The physical behaviour of the methyl group during internal rotation (torsion) is explored. Precession of the methyl group is shown to give rise to a number of the constants required to fit experimental rotational line data. Quantum chemistry calculations of the optimised molecular structures at key torsional angles provide further evidence that methyl precession occurs. [ABSTRACT FROM AUTHOR]

Sixteen intermolecular vibrational levels of the S0 state of the fluorobenzene-Ar van der Waals complex have been observed using dispersed fluorescence. The levels range up to ∼130 cm-1 in vibrational energy. The vibrational energies have been modelled using a complete set of harmonic and quartic anharmonic constants and a cubic anharmonic coupling between the stretch and long axis bend overtone that becomes near ubiquitous at higher energies. The constants predict the observed band positions with a root mean square deviation of 0.04 cm-1. The set of vibrational levels predicted by the constants, which includes unobserved bands, has been compared with the predictions of ab initio calculations, which include all vibrational levels up to 70-75 cm-1. There are small differences in energy, particularly above 60 cm-1, however, the main differences are in the assignments and are largely due to the limitations of assigning the ab initio wavefunctions to a simple stretch, bend, or combination when the states are mixed by the cubic anharmonic coupling. The availability of these experimental data presents an opportunity to extend ab initio calculations to higher vibrational energies to provide an assessment of the accuracy of the calculated potential surface away from the minimum. The intermolecular modes of the fluorobenzene-Ar2 trimer complex have also been investigated by dispersed fluorescence. The dominant structure is a pair of bands with a ∼35 cm-1 displacement from the origin band. Based on the set of vibrational modes calculated from the fluorobenzene-Ar frequencies, they are assigned to a Fermi resonance between the symmetric stretch and symmetric short axis bend overtone. The analysis of this resonance provides a measurement of the coupling strength between the stretch and short axis bend overtone in the dimer, an interaction that is not directly observed. The coupling matrix elements determined for the fluorobenzene-Ar stretch-long axis bend overtone and stretch-short axis bend overtone couplings are remarkably similar (3.8 cm-1 cf. 3.2 cm-1). Several weak features seen in the fluorobenzene-Ar2 spectrum have also been assigned. [ABSTRACT FROM AUTHOR]

We demonstrate the power of high resolution, two dimensional laser induced fluorescence (2D-LIF) spectroscopy for observing rovibronic transitions of polyatomic molecules. The technique involves scanning a tunable laser over absorption features in the electronic spectrum while monitoring a segment, in our case 100 cm-1 wide, of the dispersed fluorescence spectrum. 2D-LIF images separate features that overlap in the usual laser induced fluorescence spectrum. The technique is illustrated by application to the S1-S0 transition in fluorobenzene. Images of room temperature samples show that overlap of rotational contours by sequence band structure is minimized with 2D-LIF allowing a much larger range of rotational transitions to be observed and high precision rotational constants to be extracted. A significant advantage of 2D-LIF imaging is that the rotational contours separate into their constituent branches and these can be targeted to determine the three rotational constants individually. The rotational constants determined are an order of magnitude more precise than those extracted from the analysis of the rotational contour and we find the previously determined values to be in error by as much as 5% [G. H. Kirby, Mol. Phys. 19, 289 (1970)]. Comparison with earlier ab initio calculations of the S0 and S1 geometries [I. Pugliesi, N. M. Tonge, and M. C. R. Cockett, J. Chem. Phys. 129, 104303 (2008)] reveals that the CCSD/6-311G** and RI-CC2/def2-TZVPP levels of theory predict the rotational constants, and hence geometries, with comparable accuracy. Two ground state Fermi resonances were identified by the distinctive patterns that such resonances produce in the images. 2D-LIF imaging is demonstrated to be a sensitive method capable of detecting weak spectral features, particularly those that are otherwise hidden beneath stronger bands. The sensitivity is demonstrated by observation of the three isotopomers of fluorobenzene-d1 in natural abundance in an image taken for a supersonically cooled sample. The ability to separate some of the 13C isotopomers in natural abundance is also demonstrated. The equipment required to perform 2D-LIF imaging with sufficient resolution to resolve the rotational features of large polyatomics is available from commercial suppliers. [ABSTRACT FROM AUTHOR]

We present a comprehensive photoelectron imaging study of the O2(X 3Σg-,v′=0-6)←O2-(X 2Πg,v″=0) and O2(a 1Δg,v′=0-4)←O2-(X 2Πg,v″=0) photodetachment bands at wavelengths between 900 and 455 nm, examining the effect of vibronic coupling on the photoelectron angular distribution (PAD). This work extends the v′=1-4 data for detachment into the ground electronic state, presented in a recent communication [R. Mabbs, F. Mbaiwa, J. Wei, M. Van Duzor, S. T. Gibson, S. J. Cavanagh, and B. R. Lewis, Phys. Rev. A 82, 011401(R) (2010)]. Measured vibronic intensities are compared to Franck-Condon predictions and used as supporting evidence of vibronic coupling. The results are analyzed within the context of the one-electron, zero core contribution (ZCC) model [R. M. Stehman and S. B. Woo, Phys. Rev. A 23, 2866 (1981)]. For both bands, the photoelectron anisotropy parameter variation with electron kinetic energy, β(E), displays the characteristics of photodetachment from a d-like orbital, consistent with the πg* 2p highest occupied molecular orbital of O2-. However, differences exist between the β(E) trends for detachment into different vibrational levels of the X 3Σg- and a 1Δg electronic states of O2. The ZCC model invokes vibrational channel specific 'detachment orbitals' and attributes this behavior to coupling of the electronic and nuclear motion in the parent anion. The spatial extent of the model detachment orbital is dependent on the final state of O2: the higher the neutral vibrational excitation, the larger the electron binding energy. Although vibronic coupling is ignored in most theoretical treatments of PADs in the direct photodetachment of molecular anions, the present findings clearly show that it can be important. These results represent a benchmark data set for a relatively simple system, upon which to base rigorous tests of more sophisticated models. [ABSTRACT FROM AUTHOR]

The experimental and theoretical adiabatic ionization energies (IEs) of the rhodium-holmium bimetallic clusters RhHo2On (n=0–2) have been determined using photoionization efficiency spectroscopy and density functional theory (DFT) calculations. Both sets of data show the IE of RhHo2O to be significantly lower than the values for RhHo2 and RhHo2O2, which are found to be similar. This indicates that there are significant changes in electronic properties upon sequential addition of oxygen atoms to RhHo2. The DFT investigations show that the lowest energy neutral structures are a C2v triangle for RhHo2, a C2v planar structure for RhHo2O where the O atom is doubly bridged to the Ho–Ho bond, and a C2v nonplanar structure for RhHo2O2, where the O2 is dissociative and each O atom is doubly bridged to the Ho–Ho bond in the cluster above and below the RhHo2 trimer plane. Good correlation between the experimental and computational IE data imply that the lowest energy neutral structures calculated are the most likely isomers ionized in the molecular beam. In particular, the theoretical adiabatic IE for the dissociative RhHo2O2 structure is found to compare better with the experimentally determined value than the corresponding lowest energy O2 associative structure. [ABSTRACT FROM AUTHOR]

The photodissociation dynamics of the diazomethyl (HCNN) radical have been studied using fast radical beam photofragment translational spectroscopy. A photofragment yield spectrum was obtained for the range of 25 510–40 820 cm-1, and photodissociation was shown to occur for energies above 25 600 cm-1. The only product channel observed was the formation of CH and N2. Fragment translational energy and angular distributions were obtained at several energies in the range covered by the photofragment yield spectrum. The fragment translational energy distributions showed at least two distinct features at energies up to 4.59 eV, and were not well fit by phase space theory at any of the excitation energies studied. A revised C–N bond dissociation energy and heat of formation for HCNN, D0(HC–NN)=1.139±0.019 eV and ΔfH0(HCNN)=5.010±0.023 eV, were determined. [ABSTRACT FROM AUTHOR]

The photodissociation spectroscopy and dynamics resulting from excitation of the B 2A″←X 2A″ transition of CH2CFO have been examined using fast beam photofragment translational spectroscopy. The photofragment yield spectrum reveals vibrationally resolved structure between 29 870 and 38 800 cm-1, extending ∼6000 cm-1 higher in energy than previously reported in a laser-induced fluorescence excitation spectrum. At all photon energies investigated, only the CH2F+CO and HCCO+HF fragment channels are observed. Both product channels yield photofragment translational energy distributions that are characteristic of a decay mechanism with a barrier to dissociation. Using the barrier impulsive model, it is shown that fragmentation to CH2F+CO products occurs on the ground state potential energy surface with the isomerization barrier between CH2CFO and CH2FCO governing the observed translational energy distributions. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The photodissociation dynamics of I3- from 390 to 290 nm (3.18 to 4.28 eV) have been investigated using fast beam photofragment translational spectroscopy in which the products are detected and analyzed with coincidence imaging. At photon energies ≤3.87 eV, two-body dissociation that generates I-+I2(A 3Π1u) and vibrationally excited I2-(X 2Σu+)+I(2P3/2) is observed, while at energies >=3.87 eV, I*(2P1/2)+I2-(X 2Σu+) is the primary two-body dissociation channel. In addition, three-body dissociation yielding I-+2I(2P3/2) photofragments is seen throughout the energy range probed; this is the dominant channel at all but the lowest photon energy. Analysis of the three-body dissociation events indicates that this channel results primarily from a synchronous concerted decay mechanism. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The fluorescence excitation spectrum of the S1–S0(1B2–1A1) transition in jet-cooled toluene has been measured up to 2000 cm-1 above the origin band. Dispersed fluorescence spectra of the major features have been recorded and used to assign the levels observed in excitation. Collisional energy transfer experiments have been used to confirm assignments for some of the lower lying S1 fundamentals that were not accessible via direct optical pumping. The number of known S1 fundamentals has been extended to 13. The dispersed fluorescence spectra reveal the onset of intramolecular vibrational energy redistribution (IVR) at low S1 vibrational energies. Fluorescence lifetimes of all of the major bands observed in the excitation spectrum have been measured. The lifetimes decrease from 86 ns for 00 to 48 ns at an S1 vibrational energy of 1900 cm-1. To alleviate the confusion that exists over the mode numbering in toluene a new scheme is proposed which obviates this problem. This system is similar to that used for other substituted aromatics and should rationalize future work. © 1996 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Reports on a comparative analysis of the use between infrared multiphoton absorption (IRMPA) and ultraviolet excitation with rapid internal conversion (IC). Use of excited hexafluorobenzene molecules as basis for comparison; Viability of IRMPA on assessing molecular system types; Query on the reliability of both IRMPA and IC.

Abstract: This work investigated carbon nanotube reactions when subjected to a laser irradiation. It was found that the laser produced a fast explosion‐like result. The addition of ferrocene to the carbon nanotube powder was found to increase the decomposition temperature and reaction of photo‐initiated nanotubes. Incomplete combustion was found as a result of particle scattering and limited thermal transfer in loose samples however in confined samples a burning front can develop resulting in more complete combustion. [ABSTRACT FROM AUTHOR]

Abstract: Crude oil and hydrocarbon fuel spills are a perennial threat to aquatic environments. Inexpensive and sustainable sorbents are needed to mitigate the ecological harm of this pollution. To address this need, this study features a low‐density polysulfide polymer that is prepared by the direct reaction of sulfur and used cooking oils. Because both sulfur and cooking oils are hydrophobic, the polymer has an affinity for hydrocarbons such as crude oil and diesel fuel and can rapidly remove them from seawater. Through simple mechanical compression, the oil can be recovered and the polymer can be reused in oil spill remediation. The polysulfide is unique because it is prepared entirely from repurposed waste: sulfur is a by‐product of the petroleum industry and used cooking oil can be used as a comonomer. In this way, sulfur waste from the oil industry is used to make an effective sorbent for combatting pollution from that same sector. [ABSTRACT FROM AUTHOR]

Carbon nanotube-silicon (CNT-Si)-based heterojunction solar cells (HJSCs) are a promising photovoltaic (PV) system. Herein, few-layer black phosphorus (FL-BP) sheets are produced in N-methyl-2-pyrrolidone (NMP) using microwave-assisted liquid-phase exfoliation and introduced into the CNTs-Si-based HJSCs for the first time. The NMP-based FL-BP sheets remain stable after mixing with aqueous CNT dispersion for device fabrication. Due to their unique 2D structure and p-type dominated conduction, the FL-BP/NMP incorporated CNT-Si devices show an impressive improvement in the power conversion efficiency from 7.52% (control CNT-Si cell) to 9.37%. Our density-functional theory calculation reveals that lowest unoccupied molecular orbital (LUMO) of FL-BP is higher in energy than that of single-walled CNT. Therefore, we observed a reduction in the orbitals localized on FL-BP upon highest occupied molecular orbital to LUMO transition, which corresponds to an improved charge transport. This study opens a new avenue in utilizing 2D phosphorene nanosheets for next-generation PVs. [ABSTRACT FROM AUTHOR]

Mercury pollution threatens the environment and human health across the globe. This neurotoxic substance is encountered in artisanal gold mining, coal combustion, oil and gas refining, waste incineration, chloralkali plant operation, metallurgy, and areas of agriculture in which mercury-rich fungicides are used. Thousands of tonnes of mercury are emitted annually through these activities. With the Minamata Convention on Mercury entering force this year, increasing regulation of mercury pollution is imminent. It is therefore critical to provide inexpensive and scalable mercury sorbents. The research herein addresses this need by introducing low-cost mercury sorbents made solely from sulfur and unsaturated cooking oils. A porous version of the polymer was prepared by simply synthesising the polymer in the presence of a sodium chloride porogen. The resulting material is a rubber that captures liquid mercury metal, mercury vapour, inorganic mercury bound to organic matter, and highly toxic alkylmercury compounds. Mercury removal from air, water and soil was demonstrated. Because sulfur is a by-product of petroleum refining and spent cooking oils from the food industry are suitable starting materials, these mercury-capturing polymers can be synthesised entirely from waste and supplied on multi-kilogram scales. This study is therefore an advance in waste valorisation and environmental chemistry. [ABSTRACT FROM AUTHOR]

The time evolution of gold nanoparticle (AuNP) yields by in-situ laser irradiation from bulk gold in aqueous solutions containing the surfactant sodium dodecylsulfate (SDS) at concentrations above and below the critical micelle concentration in water is reported. These studies are augmented by transmission electron microscopy images of AuNP samples at each SDS concentration recorded after 90 min of laser irradiation. The results show that while a low concentration of SDS plays a role in the formation kinetics, there is no apparent influence of the SDS concentration around the surfactant critical micelle concentration on particle size during AuNP production. [ABSTRACT FROM AUTHOR]

Photoelectron spectra following photodetachment of the gold dicarbide anion, AuC2-, have been recorded using the velocity map imaging technique at several excitation wavelengths. The binding energy spectra show well-defined vibrational structure which, with the aid of computational calculations and Franck-Condon simulations, was assigned to a progression in the Au-C stretching mode, ν3. The experimental data indicate that the features in the spectrum correspond to a 2A′ ← 3A′ transition, involving states which we calculate to have bond angles ∼147° but with a low barrier to linearity. [ABSTRACT FROM AUTHOR]

The methyl rotor dependence of a three state Fermi resonance in S1 toluene at ∼460 cm-1 has been investigated using two-dimensional laser induced fluorescence. An earlier time-resolved study has shown the Fermi resonance levels to have different energy spacings at the two lowest methyl rotor states, m = 0 and 1 [J. A. Davies, A. M. Green, and K. L. Reid, Phys. Chem. Chem. Phys. 12, 9872 (2010)]. The overlapped m = 0 and 1 spectral features have been separated to provide direct spectral evidence for the m dependence of the resonance. The resonance has been probed at m = 3a″1 for the first time and found to be absent, providing further evidence for a large change in the interaction with m. Deperturbing the resonance at m = 0 and 1 reveals that the m dependence arises through differences in the separations of the 'zero-order,' locally coupled states. It is shown that this is the result of the local 'zero-order' states being perturbed by long-range torsion-vibration coupling that shifts their energy by small amounts. The m dependence of the shifts arises from the Δm = ±3n (n = 1, 2, ...) coupling selection rule associated with torsion-rotation coupling in combination with the m2 scaling of the rotor energies, which changes the ΔE for the interaction for each m. There is also an increase in the number of states that can couple to m = 1 compared with m = 0. Consideration of the magnitude of reported torsion-rotation coupling constants suggests that this effect is likely to be pervasive in molecules with methyl rotors. [ABSTRACT FROM AUTHOR]

The technique of two-dimensional laser induced fluorescence (2D-LIF) spectroscopy has been used to observe the van der Waals complexes fluorobenzene-Ar and fluorobenzene-Ar2 in the region of their S1-S0 electronic origins. The 2D-LIF spectral images reveal a number of features assigned to the van der Waals vibrations in S0 and S1. An advantage of 2D-LIF spectroscopy is that the LIF spectrum associated with a particular species may be extracted from an image. This is illustrated for fluorobenzene-Ar. The S1 van der Waals modes observed in this spectrum are consistent with previous observations using mass resolved resonance enhanced multiphoton ionisation techniques. For S0, the two bending modes previously observed using a Raman technique were observed along with three new levels. These agree exceptionally well with ab initio calculations. The Fermi resonance between the stretch and bend overtone has been analysed in both the S0 and S1 states, revealing that the coupling is stronger in S0 than in S1. For fluorobenzene-Ar2 the 2D-LIF spectral image reveals the S0 symmetric stretch van der Waals vibration to be 35.0 cm-1, closely matching the value predicted based on the fluorobenzene-Ar van der Waals stretch frequency. Rotational band contour analysis has been performed on the fluorobenzene-Ar [formula] transition to yield a set of S1 rotational constants A′ = 0.05871 ± 0.00014 cm-1, B′ = 0.03803 ± 0.00010 cm-1, and C′ = 0.03103 ± 0.00003 cm-1. The rotational constants imply that in the S1 00 level the Ar is on average 3.488 Å from the fluorobenzene centre of mass and displaced from it towards the centre of the ring at an angle of ∼6° to the normal. The rotational contour for fluorobenzene-Ar2 was predicted using rotational constants calculated on the basis of the fluorobenzene-Ar geometry and compared with the experimental contour. The comparison is poor which, while due in part to expected saturation effects, suggests the presence of another band lying beneath the contour. [ABSTRACT FROM AUTHOR]

The photodissociation dynamics of NCO have been examined using fast beam photofragment translational spectroscopy. Excitation of the 1[sub 0][sup 2], 3[sub 0][sup 1], and 1[sub 0][sup 2]3[sub 0][sup 2] transitions of the B˜ [sup 2]Π←X˜ [sup 2]Π band produces N([sup 4]S)+CO photofragments exclusively, while excitation of the 1[sub 0][sup 3]3[sub 0][sup 3] transition yields primarily N([sup 2]D)+CO photoproducts. The translational energy [P(E[sub T])] distributions yield D[sub 0](N-CO)=2.34±0.03 eV, and ΔH[sub f,0][sup 0](NCO)=1.36±0.03 eV. The P(E[sub T]) distributions exhibit vibrationally resolved structure reflecting the vibrational and rotational distributions of the CO product. The N([sup 2]D)+CO distribution can be fit by phase space theory (PST), while the higher degree of CO rotational excitation for N([sup 4]S)+CO products implies that NCO passes through a bent geometry upon dissociation. The P(E[sub T]) distributions suggest that when the B˜ [sup 2]Π←X˜ [sup 2]Π band is excited, NCO undergoes internal conversion to its ground electronic state prior to dissociation. Excitation of NCO at 193 nm clearly leads to the production of N([sup 2]D)+CO fragments. While conclusive evidence for the higher energy O([sup 3]P)+CN(X [sup 2]Σ[sup +]) channel was not observed, the presence of this dissociation pathway could not be excluded. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Our examination of over 230 worldwide opal samples shows that X-ray diffraction (XRD) remains the best primary method for delineation and classification of opal-A, opal-CT and opal-C, though we found that mid-range infra-red spectroscopy provides an acceptable alternative. Raman, infra-red and nuclear magnetic resonance spectroscopy may also provide additional information to assist in classification and provenance. The corpus of results indicated that the opal-CT group covers a range of structural states and will benefit from further multi-technique analysis. At the one end are the opal-CTs that provide a simple XRD pattern ("simple" opal-CT) that includes Ethiopian play-of-colour samples, which are not opal-A. At the other end of the range are those opal-CTs that give a complex XRD pattern ("complex" opal-CT). The majority of opal-CT samples fall at this end of the range, though some show play-of-colour. Raman spectra provide some correlation. Specimens from new opal finds were examined. Those from Ethiopia, Kazakhstan, Madagascar, Peru, Tanzania and Turkey all proved to be opal-CT. Of the three specimens examined from Indonesian localities, one proved to be opal-A, while a second sample and the play-of-colour opal from West Java was a "simple" Opal-CT. Evidence for two transitional types having characteristics of opal-A and opal-CT, and "simple" opal-CT and opal-C are presented. [ABSTRACT FROM AUTHOR]

With the Minamata Convention coming into force this year, there is a growing requirement for low‐cost sorbents for mercury pollution. Thus, a polysulfide was prepared by the co‐polymerization of sulfur and canola oil. As sulfur is a byproduct of the petroleum industry and used cooking oils are suitable starting materials, the resulting sorbent can be prepared entirely from waste. This high‐sulfur rubber was effective in trapping diverse forms of mercury including mercury metal, inorganic mercury, and organomercury compounds. More information can be found in the Full Paper by J. M. Chalker et al. on page 16219. [ABSTRACT FROM AUTHOR]