Unveiling temporal correlations characteristic of a phase transition in the output intensity of a fiber laser

We use advanced statistical tools of time-series analysis to characterize the dynamical complexity of the transition to optical wave turbulence in a fiber laser. Ordinal analysis and the horizontal visibility graph applied to the experimentally measured laser output intensity reveal the presence of temporal correlations during the transition from the laminar to the turbulent lasing regimes. Both methods unveil coherent structures with well-defined time scales and strong correlations both, in the timing of the laser pulses and in their peak intensities. Our approach is generic and may be used in other complex systems that undergo similar transitions involving the generation of extreme fluctuations.

Structure, energetics and reactions of metal cation complexes of dipeptides in the gas phase

Structure, energetics and reactions of ions in the gas phase can be revealed by mass spectrometry techniques coupled to ions activation methods. Ions can gain enough energy for dissociation by absorbing IR light photons introduced by an IR laser to the mass spectrometer. Also collisions with a neutral molecule can increase the internal energy of ions and provide the dissociation threshold energy. Infrared multiple photon dissociation (IRMPD) or sustained off-resonance irradiation collision-induced dissociation (SORI-CID) methods are combined with Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometers where ions can be held at low pressures for a long time. The outcome of ion activation techniques especially when it is compared to the computational methods results is of great importance since it provides useful information about the structure, thermochemistry and reactivity of ions of interest. In this work structure, energetics and reactivity of metal cation complexes with dipeptides are investigated. Effect of metal cation size and charge as well as microsolvation on the structure of these complexes has been studied. Structures of bare and hydrated Na and Ca complexes with isomeric dipeptides AlaGly and GlyAla are characterized by means of IRMPD spectroscopy and computational methods. At the second step unimolecular dissociation reactions of singly charged and doubly charged multimetallic complexes of alkaline earth metal cations with GlyGly are examined by CID method. Also structural features of these complexes are revealed by comparing their IRMPD spectra with calculated IR spectra of possible structures. At last the unimolecular dissociation reactions of Mn complexes are studied. IRMPD spectroscopy along with computational methods is also employed for structural elucidation of Mn complexes. In addition the ion-molecule reactions of Mn complexes with CO and water are explored in the low pressures obtained in the ICR cell.

Selective gas phase hydrogenation of p-nitrobenzonitrile to p-aminobenzonitrile over zirconia supported gold

We acknowledge the contribution of Dr. N. Perret to this work. EPSRC support for free access to the TEM/SEM facility at the University of St. Andrews and financial support to Dr. X. Wang and Y. Hao through the Overseas Research Students Award Scheme (ORSAS) are also acknowledged.

Palladium Sulfide – A Highly Selective Catalyst for the Gas Phase Hydrogenation of Alkynes to Alkenes

Acknowledgements The support of the Spanish Government (projects CTQ2014-52956-C3-2-R and CTQ2014-52956-C3-3-R) is recognized.

Effect of support redox character on catalytic performance in the gas phase hydrogenation of benzaldehyde and nitrobenzene over supported gold

Peer reviewed

Selective gas phase hydrogenation of nitroarenes over Mo2C supported Au-Pd

Peer reviewed

Investigating optical complexity of the phase transition in the intensity of a fibre laser radiation

Fibre lasers have been shown to manifest a laminar-to-turbulent transition when increasing its pump power. In order to study the dynamical complexity of this transition we use advanced statistical tools of time-series analysis. We apply ordinal analysis and the horizontal visibility graph to the experimentally measured laser output intensity. This reveal the presence of temporal correlations during the transition from the laminar to the turbulent lasing regimes. Both methods allow us to unveil coherent structures with well defined time-scales and strong correlations both, in the timing of the laser pulses and in their peak intensities.

Air-sea transfer of gas phase controlled compounds

Gases in the atmosphere/ocean have solubility that spans several orders of magnitude. Resistance in the molecular sublayer on the waterside limits the air-sea exchange of sparingly soluble gases such as SF6 and CO2. In contrast, both aerodynamic and molecular diffusive resistances on the airside limit the exchange of highly soluble gases (as well as heat). Here we present direct measurements of air-sea methanol and acetone transfer from two open cruises: the Atlantic Meridional Transect in 2012 and the High Wind Gas Exchange Study in 2013. The transfer of the highly soluble methanol is essentially completely airside controlled, while the less soluble acetone is subject to both airside and waterside resistances. Both compounds were measured concurrently using a proton-transfer-reaction mass spectrometer, with their fluxes quantified by the eddy covariance method. Up to a wind speed of 15 m s-1, observed air-sea transfer velocities of these two gases are largely consistent with the expected near linear wind speed dependence. Measured acetone transfer velocity is ~30% lower than that of methanol, which is primarily due to the lower solubility of acetone. From this difference we estimate the "zero bubble" waterside transfer velocity, which agrees fairly well with interfacial gas transfer velocities predicted by the COARE model. At wind speeds above 15 m s-1, the transfer velocities of both compounds are lower than expected in the mean. Air-sea transfer of sensible heat (also airside controlled) also appears to be reduced at wind speeds over 20 m s-1. During these conditions, large waves and abundant whitecaps generate large amounts of sea spray, which is predicted to alter heat transfer and could also affect the air-sea exchange of soluble trace gases. We make an order of magnitude estimate for the impacts of sea spray on air-sea methanol transfer.

Air-sea transfer of gas phase controlled compounds

Gases in the atmosphere/ocean have solubility that spans several orders of magnitude. Resistance in the molecular sublayer on the waterside limits the air-sea exchange of sparingly soluble gases such as SF6 and CO2. In contrast, both aerodynamic and molecular diffusive resistances on the airside limit the exchange of highly soluble gases (as well as heat). Here we present direct measurements of air-sea methanol and acetone transfer from two open cruises: the Atlantic Meridional Transect in 2012 and the High Wind Gas Exchange Study in 2013. The transfer of the highly soluble methanol is essentially completely airside controlled, while the less soluble acetone is subject to both airside and waterside resistances. Both compounds were measured concurrently using a proton-transfer-reaction mass spectrometer, with their fluxes quantified by the eddy covariance method. Up to a wind speed of 15 m s-1, observed air-sea transfer velocities of these two gases are largely consistent with the expected near linear wind speed dependence. Measured acetone transfer velocity is ~30% lower than that of methanol, which is primarily due to the lower solubility of acetone. From this difference we estimate the "zero bubble" waterside transfer velocity, which agrees fairly well with interfacial gas transfer velocities predicted by the COARE model. At wind speeds above 15 m s-1, the transfer velocities of both compounds are lower than expected in the mean. Air-sea transfer of sensible heat (also airside controlled) also appears to be reduced at wind speeds over 20 m s-1. During these conditions, large waves and abundant whitecaps generate large amounts of sea spray, which is predicted to alter heat transfer and could also affect the air-sea exchange of soluble trace gases. We make an order of magnitude estimate for the impacts of sea spray on air-sea methanol transfer.

Continuous flow gas phase photoreforming of methanol at elevated reaction temperatures sensitised by Pt/TiO2

Gas phase photoreforming of methanol using a Pt/TiO2 photocatalyst has been performed under flow conditions at elevated temperatures. Comparing the activity of the reforming process as a function of temperature under dark and irradiated conditions shows a significant enhancement in the rate of H2 production using the photo-assisted conditions at temperatures between 100-140 °C. At higher temperatures, the effect of irradiation is small with the process dominated by the thermal process. Deactivation of the catalyst was observed under irradiation but the catalyst was easily regenerated using an oxygen treatment at 120 °C. Diffuse Reflectance Infra-red Fourier Transform Spectroscopy (DRIFTS) showed that the activity of the catalyst could be correlated with the presence of the photogenerated trapped electrons. In addition, lower amounts of CO adsorbed on Pt, compared to those observed in the dark reaction, were found for the UV-irradiated systems. It is proposed that CO and adsorbed intermediates, such as formate, can act as inhibitors in the photoreforming process and this is further supported by the observation that, before and after the regeneration process in O2, the CO and surface adsorbed organic intermediate products are removed and the activity is recovered.

The dispersed laser-induced fluorescence spectrum of gas-phase C60 at 308 nm

info:eu-repo/semantics/published

Mannich-Type reactions in the Gas-Phase: the addition of Enol Silanes to cyclic N-Acyliminium Ions

The intrinsic gas-phase reactivity of cyclic N-acyliminium ions in Mannich-type reactions with the parent enol silane, vinyloxytrimethylsilane, has been investigated by double- and triple-stage pentaquadrupole mass spectrometric experiments. Remarkably distinct reactivities are observed for cyclic N-acyliminium ions bearing either endocyclic or exocyclic carbonyl groups. NH-Acyliminium ions with endocyclic carbonyl groups locked in s-trans forms participate in a novel tandem N-acyliminium ion reaction:  the nascent adduct formed by simple addition is unstable and rearranges by intramolecular trimethylsilyl cation shift to the ring nitrogen, and an acetaldehyde enol molecule is eliminated. An NSi(CH3)3-acyliminium ion is formed, and this intermediate ion reacts with a second molecule of vinyloxytrimethylsilane by simple addition to form a stable acyclic adduct. N-Acyl and N,N-diacyliminium ions with endocyclic carbonyl groups, for which the s-cis conformation is favored, react distinctively by mono polar [4+ + 2] cycloaddition yielding stable, ressonance-stabilized cycloadducts. Product ions were isolated via mass-selection and structurally characterized by triple-stage mass spectrometric experiments. B3LYP/6-311G(d,p) calculations corroborate the proposed reaction mechanisms.

Intrinsic gas-phase electrophilic reactivity of Ccclic N-alkyl- and N-acyliminium ions

he intrinsic gas-phase reactivity of cyclic N-alkyl- and N-acyliminium ions toward addition of allyltrimethylsilane (ATMS) has been compared using MS2 and MS3 pentaquadrupole mass spectrometric experiments. An order of electrophilic reactivity has been derived and found to agree with orders of overall reactivity in solution. The prototype five-membered ring N-alkyliminium ion 1a and its N-CH3 analogue 1b, as well as their six-membered ring analogues 1c and 1d, lack N-acyl activation and they are, accordingly, inert toward ATMS addition. The five- and six-membered ring N-acyliminium ions with N-COCH3 exocycclic groups, 3a and 3b, respectively, are also not very reactive. The N-acyliminium ions 2a and 2c, with s-trans locked endocyclic N-carbonyl groups, are the most reactive followed closely by 3c and 3d with exocyclic (and unlocked) N-CO2CH3 groups. The five-membered ring N-acyliminium ions are more reactive than their six-membered ring analogues, that is:  2a > 2c and 3c > 3d. In contrast with the high reactivity of 2a, its N-CH3 analogue 2b is inert toward ATMS addition. For the first time, the transient intermediates of a Mannich-type condensation reaction were isolatedthe β-silyl cations formed by ATMS addition to N-acyliminium ionsand their intrinsic gas-phase behavior toward dissociation and reaction with a nucleophile investigated. When collisionally activated, the β-silyl cations dissociate preferentially by Grob fragmentation, that is, by retro-addition. With pyridine, they react competitively and to variable extents by proton transfer and by trimethylsilylium ion abstractionthe final and key step postulated for α-amidoalkylation. Becke3LYP/6-311G(d,p) reaction energetics, charge densities on the electrophilic C-2 site, and AM1 LUMO energies have been used to rationalize the order of intrinsic gas-phase electrophilic reactivity of cyclic iminium and N-acyliminium ions.