Reaction Channels Research Articles

Mechanism and Reaction Channels of Iron-Catalyzed Primary Amination of Alkenes by Hydroxylamine Reagents

Iron-catalyzed N-transfer by hydroxylamine-derived reagents has emerged as an appealing method for the straightforward synthesis of unprotected primary amines. Here, we studied the detailed reaction mechanism of the FePc-catalyzed aminofunctionalization of styrene with AcO-NH3OTf and PivO-NH3OTf by quantum chemical calculations and mass spectrometry experiments. An inner-sphere heterolytic N–O cleavage mechanism was proposed for the hydroxylamine activation. It affords an unprotected iron-amido species ([PcFeNH2]+), which has been detected by mass spectrometry. The iron-amido species acts as the active aminating intermediate and reacts with styrene to form a radical intermediate, followed by nucleophilic addition with methanol to generate the product. Electronic structure analysis revealed σ- and π-channels in the N-transfer process for the iron-amido species. This reported iron–nitrogen complex resembles the iron-oxo species to possess both σ- and π-channels, unveiling the mechanistic connections with iron-oxo chemistry.

Generic method to assess transmutation feasibility for nuclear waste treatment and application to irradiated graphite

Graphite-moderated nuclear reactors have already produced more than 250,000 tons of irradiated nuclear graphite, or i-graphite, world-wide. The sustainability of this technology relies on the end-of-life management of its moderator, which is activated into a long-lived, low or intermediate-level nuclear waste, by neutron fluxes, during operating time. In particular, carbon-14 is created. Nuclear transmutation, enabled by laser-driven particle acceleration, has been envisioned as a potential novel treatment scheme for long-lived nuclear waste. By triggering controlled nuclear reactions with energetic particles, long-lived radio-nuclides could be transformed into short-lived or stable isotopes. Such a system could treat the carbon-14 nuclei trapped within the i-graphite matrix, an isotope which is difficult to isolate by other means. This work performs a quantitative preliminary study of this transmutation scheme, in order to assess its feasibility at an industrial scale. The method used can be transposed to assess any transmutation scheme using a beam of particles directly sent on the material to be treated. First, a nuclear interaction channel which transmutes carbon-14 nuclei without creating new long-lived radio-nuclides is identified. It consists in the choice of a type of particle, among which protons, γ photons and neutrons can all be accelerated by laser–matter interaction; and it is completed by the adequate energy at which this particle must be sent on i-graphite. To that end, the nuclear cross-sections of carbon-12, carbon-13 and carbon-14 are reviewed, neglecting other impurities in i-graphite. Then, based on the interaction channel identification, the energy cost of this scheme is estimated. Protons between 1 and 5MeV make it possible to transmute carbon-14 without creating any new long-lived activity. However, our result show that, even in this favourable reaction channel, the transmutation energy cost is too high for an i-graphite transmutation scheme to be industrially feasible.

Quantification of the 35Cl[formula omitted] reaction channel

The evaluated 35Cl(n,p) cross sections in the ENDF/B-VIII.0 nuclear data library remain uncertain because of the lack of measured data in the 100–600 keV neutron energy range. In this energy region, the R-matrix analysis relies heavily on estimated (n,p) partial widths and level density information. This resulted in significant differences for the evaluated cross sections and predicted reactivity in nuclear reactor applications with respect to previous nuclear data libraries. This paper presents a methodology to quantify the cross sections for the 35Cl(n,p) reaction channel from the combination of measured total cross sections and model calculations.

Degradation of Bisphonel AF (BPAF) by zero-valent iron activated persulfate: Kinetics, mechanisms, theoretical calculations, and effect of co-existing chloride

The removal of Bisphonel AF (BPAF) by zero-valent iron activated persulfate (Fe0/PS) system was systematically evaluated in this work. 30.0 μM BPAF was removed by 94.4% in 60 min of treatment under optimal conditions of pH = 3.0 and [PS] = [Fe0] = 3.0 mM. Cl− significantly accelerated the removal of BPAF, resulting from accelerated Fe2+ release and reactive chlorine species (RCS) formation. Liquid chromatography-time-of-flight-mass spectrometry identified thirteen degradation products, and bond breaking, coupling reactions, hydroxylation and sulfate addition were considered as the major transformation pathways. When Cl− was present, six new chlorinated byproducts were also generated. Based on density functional theory (DFT) calculations, the occurrence of radical addition reactions was verified and the preferential reaction channels were determined. Significantly BPAF degradation products were less toxic, according to toxicity assessment by the ECOSAR program. Moreover, a high removal efficiency of BPAF (>90%) was also obtained in the three actual water matrixes. The present work demonstrates the feasibility of Fe0/PS system for treating BPAF, which could also provide new insights into the influence of coexisting Cl− on the environmental fate of organic pollutants in sulfate radicals based advanced oxidation processes.

Ultrafast Excited State Aromatization in Dihydroazulene

Excited-state aromatization dynamics in the photochemical ring opening of dihydroazulene (DHA) is investigated by nonadiabatic molecular dynamics simulations in connection with the mixed-reference spin-flip (MRSF)-TDDFT method. It is found that, in the main reaction channel, the ring opening occurs in the excited state in a sequence of steps with increasing aromaticity. The first stage lasting ca. 200 fs produces an 8π semiaromatic S1 minimum (S1,min) through an ultrafast damped bond length alternation (BLA) movement synchronized with a partial planarization of the cycloheptatriene ring. An additional ca. 200 fs are required to gain the vibrational energy needed to overcome a ring-opening transition state characterized by an enhanced Baird aromaticity. Unlike other BLA motions of ππ* state, it was shown that their damping is a characteristic feature of aromatic bond-equalization process. In addition, some minor channels of the reaction have also been discovered, where noticeably higher barriers of the S1 non/antiaromatic transition structures must be surmounted. These anti-Baird channels led to reformation of DHA or other closed-ring products. The observed competition between the Baird and anti-Baird channels suggests that the quantum yield of photochemical products can be controllable by tipping their balance. Hence, here we suggest including the concept of anti-Baird, which would expand the applicability of Baird rule to much broader situations.

The Sequence Makes the Difference: On the Reaction of Phosphorus‐centered Biradical [⋅P(μ‐N‐tBuPh3C)2P⋅] with Tolan

AbstractThe biradical [⋅P(μ‐N‐tBuPh3C)2P⋅] (6T) can be generated by reduction of a cyclic dichlorophosphane, [ClP(μ‐N‐tBuPh3C)2PCl], utilizing magnesium. If this biradical is treated with alkynes, e. g. tolan, Ph−C≡C−Ph, the addition product, a [2.1.1.] bicyclic species, [P(μ‐N‐tBuPh3C)2P(Ph−C=C−Ph)] (7), is obtained. However, if the reduction process with magnesium is carried out in the presence of tolan the reaction mixture finds a different reaction channel, ultimately yielding a magnesium(II) double salt, including a [Mg(THF)2]2+ cation with a [tBuPh3C−N−P−N−CtBuPh3]− and a novel tolan‐stabilized [(PhC=CPh)P−N−P(PhC=CPh)]− anion as counterions. This novel anion can also be conceived as anionic [2.2.1] bicycle with a [N]− ion trans‐annular bridging a 1,4‐diphosphabenzene.

Differential cross–section measurements and R-Matrix calculations for proton elastic scattering on natMg in the energy range Ep,lab = 2.70–4.25 MeV, suitable for EBS

In the current work the first coherent set of differential cross section values for the natMg(p,p0)natMg elastic scattering covering the Ep,lab = 2700–4250 keV energy range is presented for 6 backscattering detection angles (120°, 130°, 140°, 150°, 160° and 170°). R-Matrix calculations were implemented using the AZURE 2.0 code [1] in an attempt to reproduce the obtained experimental data, whilst taking into account the 24Mg(p,p1)24Mg reaction channel. Both results are suitable for EBS and other IBA applications and, furthermore, they form a basis for a future expansion of the current SigmaCalc [2] evaluation, once more experimental data become available. The measurements were performed in the 5.5 MV TN11 HV Tandem Accelerator and the high precision goniometer of N.C.S.R. ‘Demokritos’, Athens, Greece. The experimental and data analysis procedures are presented in detail, along with the process behind the implementation of the R-Matrix calculations.

Asymmetric transfer hydrogenation of ketones catalyzed by chiral macrocyclic cobalt(II) complexes

Using easily available CoBr2 and chiral cyclic PxNy-type ligands as starting materials, novel chiral cyclic cobalt(II) complexes could be conveniently prepared. Furthermore, we obtained the single crystals suitable for X-ray diffraction to confirm the structures of these cobalt(II) complexes. The asymmetric transfer hydrogenation (ATH) of ketones catalyzed by these well-designed cobalt(II) complexes was investigated. Among them, cobalt(II) complex containing chiral macrocyclic iminophosphine ligand CyP2N4 exhibited high catalytic activity and enantioselectivity (up to 99% ee). Density functional theory (DFT) calculations suggested that cobalt(II) complex (R,R,R',R')-CyP2N4-Co(II) (C1) is easier to form metal hydride, which is the key intermediate during the enantioselective transfer hydrogenation reaction. Study results also revealed that the unique macrocyclic structure of complex C1 could form a special microenvironment around cobalt ion. Therefrom the substrate coordinated with the central metal along this specific reaction channel during the asymmetric catalytic reaction, resulting high enantioselectivity.

Study of Low- and Intermediate-Temperature Oxidation Kinetics of Diethyl Ether in a Supercritical Pressure Jet-Stirred Reactor.

Growing demand for low-emission and high-efficiency propulsion systems spurs interest in understanding low-temperature and ultra-high-pressure combustion of alternative biofuels like diethyl ether (DEE). In this study, DEE oxidation experiments are performed at 10 and 100 atm, over a temperature range of 400-900 K, at fuel-lean, stoichiometric, and fuel-rich conditions by using a supercritical pressure jet-stirred reactor (SP-JSR). The experimental data show that DEE is very reactive and exhibits an uncommon low-temperature oxidation behavior with two negative temperature coefficient (NTC) zones. The first NTC zone is mainly governed by the competition reactions of QOOH + O2 = O2QOOH and QOOH = 2CH3CHO + OH, while the second one is mainly governed by the competition reactions of R + O2 = RO2 and the β-scission reaction of fuel radical R. It is shown that the increase of pressure stabilizes RO2 and promotes HO2 chemistry. Moreover, the branching ratios of β-scission reactions of R and QOOH decrease. As a result, it is shown that, with the increase of pressure, both NTC zones become weaker at 100 atm. In addition, the intermediate-temperature oxidation is shifted considerably to lower temperature at 100 atm. The existing DEE model in the literature well predicts the experimental data at low temperature; however, it underpredicts the fuel consumptions at intermediate temperature. The H2/O2 subset in the existing DEE model is updated in this study based on the Princeton updated HP-Mech, including the singlet/triplet competing channels of HO2 related reactions. The updated model improves the overall predictability of key species, especially at intermediate temperature.

The quantum dynamics of H2 on Cu(111) at a surface temperature of 925K: Comparing state-of-the-art theory to state-of-the-art experiments 2.

State-of-the-art 6D quantum dynamics simulations for the dissociative chemisorption of H2 on a thermally distorted Cu(111) surface, using the static corrugation model, were analyzed to produce several (experimentally available) observables. The expected error, especially important for lower reaction probabilities, was quantified using wavepackets on several different grids as well as two different analysis approaches to obtain more accurate results in the region where a slow reaction channel was experimentally shown to be dominant. The lowest reaction barrier sites for different thermally distorted surface slabs are shown to not just be energetically, but also geometrically, different between surface configurations, which can be used to explain several dynamical effects found when including surface temperature effects. Direct comparison of simulated time-of-flight spectra to those obtained from state-of-the-art desorption experiments showed much improved agreement compared to the perfect lattice BOSS approach. Agreement with experimental rotational and vibrational efficacies also somewhat improved when thermally excited surfaces were included in the theoretical model. Finally, we present clear quantum effects in the rotational quadrupole alignment parameters found for the lower rotationally excited states, which underlines the importance of careful quantum dynamical analyses of this system.

Radiation-induced transformations of matrix-isolated ethanol molecules at cryogenic temperatures: an FTIR study.

Ethanol (C2H5OH) is one of the most common alcohol molecules observed in various space media (molecular clouds, star formation regions, and, highly likely, interstellar ices), where it is exposed to light and ionizing radiation, leading to more complex organic molecules and eventually to the biologically important species. To better understand the radiation-induced evolution of ethanol molecules in icy media, we have examined the transformations of isolated C2H5OH and C2D5OH under the action of X-rays and vacuum ultraviolet (VUV) radiation in solid inert matrices (Ne, Ar, Kr, and Xe) at 4.4 K using Fourier transform infrared (FTIR) spectroscopy. The results obtained with X-ray irradiation demonstrate the formation of a variety of radiolysis products corresponding to dehydrogenation (CH3CHOH˙, CH3CHO, CH2CHOH, CH3CO˙, H2CCO-H2, H2CCO, HCCO˙, CCO) and C-C bond rupture (H2CO, HCO˙, CO, CH4, and CH3˙). The absorptions of the CH3CHOH˙ radical related to the CCO stretching (the bands at 1249.1, 1247.0, 1246.2, and 1245.1 cm-1, in Ne, Ar, Kr, and Xe, respectively) were first tentatively characterized on the basis of comparison with available computational data. In addition, the C2H2⋯H2O complex, which corresponds to dehydrogenation, was found followed by C-O bond cleavage. The results were confirmed by experiments with isotopic substitution. It was found that dehydrogenation strongly predominated in a xenon matrix, while skeleton bond rupture is more feasible in neon and argon. The matrix effect was attributed to a significant role of "hot" reaction channels in neon and argon, which are efficiently quenched due to relaxation in more polarizable xenon. The VUV photolysis (185 nm) in Ar and Xe matrices yields a similar set of products, except for CH3CHOH˙ and CH2CHOH, which were not found (the nonobservation of the former species may be explained by its efficient secondary photolysis). The plausible mechanisms of product formation and astrochemical implications of the results are discussed.

Cross Section Measurements of (n,x) Reactions at 17.9 and 18.9 MeV Using Highly Enriched Ge Isotopes

Nine neutron induced reactions on Ge isotopes (70Ge(n,2n)69Ge, 76Ge(n,2n)75Ge, 73Ge(n,p)73Ga, 72Ge(n,p)72Ga, 73Ge(n,d/np)72Ga, 74Ge(n,d/np)73Ga, 74Ge(n,α)71mZn, 72Ge(n,α)69mZn, 73Ge(n,nα)69mZn) have been measured in this work at energies 16.4-18.9 MeV. For these reactions, most of the experimental datasets in literature were obtained with a natGe target. However, the residual nucleus produced by some reaction channels can also be produced from neighboring isotopes, acting as a contamination for the measured reactions. This contribution must be subtracted, based on theoretical calculations, bearing their own uncertainties. The use of enriched targets however, does not suffer from such contaminations, leading to accurate experimental results. In this scope, five highly isotopically enriched Ge samples have been used in this work. The quasi-monoenergetic neutron beams were produced via the 3H(d,n)4He reaction at the 5.5 MV Tandem Van de Graaff accelerator of N.C.S.R. ‘Demokritos’. The cross section of these nine reactions were measured using the activation method, with respect to the 27Al(n,α)24Na reference reaction.

Experimental study of 37Cl(α,n)40K reaction in order to constrain the reaction rate of destruction of 40K in stars

40K is one of the main isotopes responsible for the radiogenic heating of the mantle in Earth-like exoplanets [1] and hence, plays a very important role in the internal geophysical dynamics of a planet. The abundance of 40K in the mantle and the core of such planets is not always possible to be determined by astrophysical observations, although constraining the nuclear reaction rates of 40K during stellar evolution can also lead to constraining the present amount of 40K in these planets, which will improve our understanding on the habitability potential of Earth-like exoplanets. This study aims to constrain the 40K(n,α)37Cl reaction rate, one of the two major destruction paths of 40K in stellar nucleosynthesis,by measuring the reverse reaction 37Cl(α,n)40K and applying the principle of detailed balance as we have done before for the 40K (40K(n,p)40Ar reaction rate) [2]. During the first set of measurements we performed differential cross-section measurements of the 37Cl(α,n1γ)40K, 37Cl(α,n2γ)40K and 37Cl(α,n3γ)40K reaction channels, for six different center of mass energies in the range between 5.1 and 5.4 MeV. The experiment took place at the Edwards Accelerator Laboratory of Ohio University. The gamma rays from the reaction channels mentioned above were detected by two LaBr3 scintillators. Using the swinger facility to change the angle of the beam-target system with respect to the detection system, we were able to take measurements for the differential cross-section at six different angles between 20° and 120° in the lab system.

Gamow Shell Model Description of \(^7\)Li and Elastic Scattering Reaction \(^4\)He(\(^3\)H,\(^3\)H)\(^4\)He

Spectrum of $^7$Li and elastic scattering reaction $^4$He($^3$H, $^3$H)$^4$He are studied using the unified description of the Gamow shell model in the coupled-channel formulation (GSMCC). The reaction channels are constructed using the cluster expansion with the two mass partitions [$^4$He + $^3$H], [$^6$Li + n].

New prebiotic molecules in the interstellar medium from the reaction between vinyl alcohol and CN radicals: unsupervised reaction mechanism discovery, accurate electronic structure calculations and kinetic simulations.

Vinyl alcohol (VyA) and cyanide (CN) radicals are relatively abundant in the interstellar medium (ISM). VyA is the enolic tautomer of acetaldehyde and has two low-lying conformers, characterized by the syn or anti placement of hydroxyl hydrogen with respect to the double bond. In this paper, we present a gas-phase model of the barrierless reactions of both VyA's conformers with CN employing accurate quantum chemical computations in the framework of a master equation approach based on the transition state theory. Our results indicate that both VyA conformers feature a similar reactivity with CN, starting with a barrierless addition to the double bond and followed by different isomerization, dissociation, and/or hydrogen elimination steps. The rate constants computed for temperatures up to 600 K show that several reaction channels are open even under the harsh conditions of the ISM, with the favoured one providing the first feasible formation route of a prebiotic molecule not yet detected in the ISM, namely cyanoacetaldehyde. This finding suggests looking for cyanoacetaldehyde in regions where both VyA and CN have already been detected, like, e.g., Sagittarius B2N or G+0.693-0.027.

Nuclear data activities at GELINA

Over the last decade, efforts were made to improve the performance of the experimental set-ups at the Geel Electron Linear Accelerator (GELINA) neutron time-of-flight facility of the European Commission Joint Research Centre (EC-JRC). These efforts, which result in an improved quality of neutroninduced cross section data for many reaction channels like elastic, inelastic, capture, fission, etc., relate to the accelerator, the measurement setups and the data reduction and analysis procedures. This paper presents a summary of the data produced in the last years at GELINA for nuclear energy applications. Most of the work has been performed as part of the EUFRAT open-access program.

Proton capture on stored radioactive 118Te ions

Experimental determination of the cross sections of proton capture on radioactive nuclei is extremely difficult. Therefore, it is of substantial interest for the understanding of the production of the p-nuclei. For the first time, a direct measurement of proton-capture cross sections on stored, radioactive ions became possible in an energy range of interest for nuclear astrophysics. The experiment was performed at the Experimental Storage Ring (ESR) at GSI by making use of a sensitive method to measure (p,γ) and (p,n) reactions in inverse kinematics. These reaction channels are of high relevance for the nucleosyn-thesis processes in supernovae, which are among the most violent explosions in the universe and are not yet well understood. The cross section of the 118Te(p,γ) reaction has been measured at energies of 6 MeV/u and 7 MeV/u. The heavy ions interacted with a hydrogen gas jet target. The radiative recombination process of the fully stripped 118Te ions and electrons from the hydrogen target was used as a luminosity monitor. An overview of the experimental method and preliminary results from the ongoing analysis will be presented.

Potential energy surfaces for singlet and triplet states of the LiH2+ system and quasi-classical trajectory cross sections for H + LiH+ and H+ + LiH.

A new set of six accurate ab initio potential energy surfaces (PESs) is presented for the first three singlet and triplet states of LiH2+ (1,21A', 11A'', 1,23A', and 13A'' states, where four of them are investigated for the first time), which have allowed new detailed studies gaining a global view on this interesting system. These states are relevant for the study of the most important reactions of lithium chemistry in the early universe. More than 45 000 energy points were calculated using the multi-reference configuration interaction level of theory using explicitly correlated methods (ic-MRCI-F12), and the results obtained for each individual electronic state were fitted to an analytical function. Using quasiclassical trajectories and considering the initial diatomic fragment in the ground rovibrational state, we have determined the integral cross sections for the H + LiH+(X2Σ+, C2Π) and H+ + LiH(X1Σ+, B1Π) reactions. In these calculations all available reaction channels were considered: the chemically most important H or H+ transfer/abstraction as well as atom exchange and collision induced dissociation for up to 1.0 eV of collision energy.

Advanced kinetic calculations with multi-path variational transition state theory for reactions between dimethylamine and nitrogen dioxide in atmospheric and combustion temperature ranges.

Rate constants of the reactions between dimethyl amine (DMA) and NO2 are accurately determined using the advanced multi-path canonical variational theory with a small-curvature tunneling correction. To select a suitable method for the direct kinetic calculations, various combinations with nine DFT methods and seven basis sets are evaluated, and the M08-HX/ma-TZVP method is identified as the best one for the current reaction system, with a mean unsigned deviation of 1.1 kcal mol-1 in comparison with the benchmark CCSD(T)-F12/jun-cc-pVTZ. A total of 13 elementary reactions are found, but only the H-abstraction reactions are kinetically favorable and included in the kinetic calculations. The recrossing and tunneling effects are different among the various H-abstraction reaction channels as well as different reaction paths. The recrossing effects are comparably more significant for reactions at the N-site, and tunneling coefficients of the reaction channels producing a trans-HONO are the largest. The higher-energy reaction paths have much higher tunneling coefficients, which should be considered in the rate constant calculation, especially at low temperatures. Branching ratio analysis demonstrates that the most important products are CH3NCH3 + cis-HONO at 200-2000 K. Additionally, by comparing our calculations with the available literature data, the importance of the investigated reactions is discussed at combustion and atmospheric temperatures.

Laboratory hydrogenation of the photo-fragments of PAH cations: Co-evolution interstellar chemistry

To investigate co-evolution interstellar chemistry, we studied the gas-phase hydrogenation processes of possible photo-fragments of large polycyclic aromatic hydrocarbon (PAH) cations. Our experimental results show that hydrogenated photo-fragments of hexa-peri-hexabenzocoronene (HBC, C42H18) cations are efficiently formed. The predominance of even-mass fragments (C42H2n+, n = [0–9]) is observed in the photo-fragmentation experiments, while no even-odd hydrogenated mass patterns are observed in the hydrogenation experiments. We investigated the structure of these newly formed hydrogenated photo-fragments and the bonding energies for the reaction pathways with quantum chemistry calculations. We used a molecular kinetic reaction model to simulate the hydrogenation processes of the photo-fragments (e.g. C42H12+) as a function of the reaction time under the experimental conditions. We obtain the possible structure distribution of the newly formed hydrogenated fragments of C42H18+ and the infrared (IR) spectra of these possible molecules. We infer that the hydrogenation and photo-dehydrogenation channels are not reversible reaction channels. Hydrogenation tends to be more random and disorderly, with no restrictions or requirements for the carbon reaction sites of PAH species. As a result, under the co-evolution interstellar chemistry network, there is little chance that PAH compounds return to their initial state through hydrogenation processes after photo-dehydrogenation. Consequently, the hydrogenation states and forms of PAH compounds are intricate and complex in the interstellar medium (ISM).