Search Results (10)

This research presents an experimental analysis of the influence of atmospheric pressure plasma on the performance of a micro horizontal-axis wind turbine blade. The investigation was conducted using an NACA 4412 airfoil equipped with a dielectric barrier discharge (DBD) plasma actuator. The electrodes were configured asymmetrically, with a 2 mm gap and copper electrodes that are 0.20 mm in thickness. A high voltage of 6 kV was applied, resulting in a current of 0.071 mA and a power output of 0.426 W. Optical emission spectroscopy identified the excited components through the interaction of the high-voltage AC electric field with air molecules: ${\mathrm{N}}_2$, ${\mathrm{N}}_2^{+}$, ${\mathrm{O}}_2^{+}$, and O. The electrohydrodynamic force mainly results from the observed charged ions that, when accelerated by the electric field, transfer momentum to neutral molecules via collisions, leading to the formation of the observed jet plasma. The findings indicated a notable enhancement in aerodynamic performance attributable to the electrohydrodynamic (EHD) flow generated by the plasma. The estimated electrohydrodynamic force ($8.712\times {10}^{-4}$ N) is capable of maintaining the flow attached to the airfoil surface, thereby augmenting flow circulation and, consequently, enhancing the lift force. According to blade element theory, the lift and drag coefficients directly influence the torque and mechanical power generated by the wind turbine rotor. Schlieren imaging was utilized to observe alterations in air density and flow patterns. Lissajous curve analysis was used to examine the electrical discharge behavior, showing that only 7.04% of the input power was converted into heat. This indicates that nearly all input electric energy was transformed into EHD force by the atmospheric pressure plasma. Compared to traditional aerodynamic control methods, DBD actuators are a feasible alternative for small wind turbines due to their lightweight design, absence of moving parts, ability to be surface-embedded without altering blade geometry, and capacity to generate active, dynamic flow control with reduced energy consumption. Full article

The gas-phase reaction between the ethyl cation (C₂H₅⁺) and ethyne (C₂H₂) is re-investigated by measuring absolute reactive cross sections (CSs) and branching ratios (BRs) as a function of collision energy, in the thermal and hyperthermal energy range, via tandem-guided ion beam mass spectrometry under single collision conditions. Dissociative photoionization of C₂H₅Br using tuneable VUV radiation in the range 10.5–14.0 eV is employed to generate C₂H₅⁺, which has also allowed us to explore the impact of increasing (vibrational) excitation on the reactivity. Reactivity experiments are complemented by theoretical calculations, at the G4 level of theory, of the relative energies and structures of the most relevant stationary points on the reactive potential energy hypersurface (PES) and by mass-analyzed ion kinetic energy (MIKE) spectrometry experiments to probe the metastable decomposition from the [C₄H₇]⁺ PES and elucidate the underlying reaction mechanisms. Two main product channels have been identified at a centre-of-mass collision energy of $\sim 0.1$ eV: (a) C₃H₃⁺+CH₄, with BR = 0.76$\pm$0.05 and (b) C₄H₅⁺+H₂, with BR = 0.22$\pm$0.02. A third channel giving C₂H₃⁺ in association with C₂H₄ is shown to emerge at both high internal excitation of C₂H₅⁺ and high collision energies. From CS measurements, energy-dependent total rate constants in the range $4.3\times$${10}^{-11}$−$5.2\times$${10}^{-10}$ ${\mathrm{cm}}^3·$${\mathrm{molecule}}^{-1}·$${\mathrm{s}}^{-1}$ have been obtained. Theoretical calculations indicate that both channels stem from a common covalently bound intermediate, CH₃CH₂CHCH⁺, from which barrierless and exothermic pathways exist for the production of both cyclic c−C₃H₃⁺ and linear H₂CCCH⁺ isomers of the main product channel. For the minor C₄H₅⁺ product, two isomers are energetically accessible: the three-member cyclic isomer c−C₃H₂(CH₃)⁺ and the higher energy linear structure CH₂CHCCH₂⁺, but their formation requires multiple isomerization steps and passages via transition states lying only 0.11 eV below the reagents’ energy, thus explaining the smaller BR. Results have implications for the modeling of hydrocarbon chemistry in the interstellar medium and the atmospheres of planets and satellites as well as in laboratory plasmas (e.g., plasma-enhanced chemical vapor deposition of carbon nanotubes and diamond-like carbon films). Full article

Ion–molecule reactions between the neutral ethyl- (EF), isopropyl- (IF), t-butyl- (TF) and phenyl formate (PF) and proton-bound water clusters W₂H⁺ and W₃H⁺ (W = H₂O) showed that the major reaction product is water loss from the initial encounter complex, followed ultimately by the formation of the protonated formate. Collision-induced dissociation breakdown curves of the formate–water complexes were obtained as a function of collision energy and modeled to extract relative activation energies for the observed channels. Density functional theory calculations (B3LYP/6-311+G(d,p)) of the water loss reactions were consistent with reactions having no reverse energy barrier in each case. Overall, the results indicate that the interaction of formates with atmospheric water can form stable encounter complexes that will dissociate by sequential water loss to form protonated formates. Full article

In thermal cracking and collision-induced dissociation (CID) processes, molecules/ions mainly undergo cleavage reactions. In theory, the cleavage reaction is preferred for weak bonds in both processes. The present study investigates the thermal cracking and CID behavior of polar compounds in vacuum residue. By controlling the thermal reaction temperature and collision energy, different degrees of fragmentation were achieved. The molecular composition before and after the cracking process was analyzed through electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). There was a correlation between the reaction temperature and the collision energy for the average carbon number value. Both desulfurization and decarboxylation were also observed in two processes due to the low C-S bond energy and poor stability of carboxylic acid groups. Nevertheless, the two processes still had some differences in reaction selectivity. Polar species tended to be directly dealkylated down to the C1–C5 substituted aromatic core in the CID process, showing a discontinuity in the carbon number vs. double bond equivalence (DBE) distribution for the CID product. On the contrary, the carbon number distribution in the thermal reaction showed a continuously reduced trend. In summary, the CID process can qualitatively reflect the cracking behavior. However, the product structural distribution of the thermal cracking product cannot be fully predicted, especially for sidechain cracking reactions. In addition, the research results can provide a new method to realize the simulation of the thermal cracking without energy and time consumption, so as to guide the selection of the feedstock and optimization of the reaction condition. Full article

Ion–molecule reactions between neutral methyl formate (MF) and proton-bound solvent clusters W₂H⁺, W₃H⁺, M₂H⁺, E₂H⁺, and E₃H⁺ (W = water, M = methanol, and E = ethanol) showed that the major reaction product is a solvent molecule loss from the initial encounter complex, followed by the formation of protonated methyl formate (MFH⁺). Collision-induced dissociation breakdown curves of the initially formed solvent-MF proton-bound pairs and trimers were obtained as a function of collision energy and modeled to extract relative activation energies for the observed channels. Density functional theory calculations (B3LYP/6-311+G(d,p)) of the solvent loss reaction were consistent with barrierless reactions in each case. The MF(M)H⁺ ion also exhibited loss of CH₄ at higher collision energies. The reaction was calculated to proceed via the migration of the MF methyl group to form a loosely bound complex between neutral CH₄ and an ion comprising (CH₃OH)(CO₂)H⁺. Overall, the results indicate that the interaction of methyl formate with atmospheric water can form stable encounter complexes that will dissociate to form protonated methyl formate. Full article

Chiral drugs are very complex substances since individual enantiomers may differ in pharmacological and toxic effects, making it necessary to analyze enantiomers separately. In this study, we investigated the chiral differentiation of two ezetimibe enantiomers (i.e., SRS-EZM and RSR-EZM) and their mechanisms in complex with β-cyclodextrins (CDs) and metal ions as the auxiliary ligands. For this purpose, two complementary approaches have been employed: electrospray-tandem mass spectrometry (ESI-MS/MS) with collision induced dissociation (CID) and molecular modeling methods, including density functional theory (DFT) calculations and molecular dynamics (MD) simulations. The results showed a good agreement between experimental and theoretical data. It was demonstrated that SRS-EZM can be easily distinguished from RSR-EZM by applying CID in ESI-MS/MS. SRS-EZM is likely to form a more stable complex with β-CD and metal ions, and thus the [SRS-EZM]-Cu-[β-CD] cluster is more energetically difficult to separate from the SRS-EZM molecule compared with RSR-EZM. Such a difference may be attributed to the interactions between the drug molecule and the metal ion, as well as the cavity shape changes of the β-CDs upon complexation with molecular guests. Therefore, enantiomers in chiral drug can be recognized as ternary complexes of metal-analyte-β-CD by ESI-MS/MS with CID. Full article

Since its initial development in the 1970s by Phil Burke and his collaborators, the R-matrix theory and associated computer codes have become the method of choice for the calculation of accurate data for general electron–atom/ion/molecule collision and photoionization processes. The use of a non-orthogonal set of orbitals based on B-splines, now called the B-spline R-matrix (BSR) approach, was pioneered by Zatsarinny. It has considerably extended the flexibility of the approach and improved particularly the treatment of complex many-electron atomic and ionic targets, for which accurate data are needed in many modelling applications for processes involving low-temperature plasmas. Both the original R-matrix approach and the BSR method have been extended to the interaction of short, intense electromagnetic (EM) radiation with atoms and molecules. Here, we provide an overview of the theoretical tools that were required to facilitate the extension of the theory to the time domain. As an example of a practical application, we show results for two-photon ionization of argon by intense short-pulse extreme ultraviolet radiation. Full article

Thiolate-protected metal nanoclusters have highly size- and structure-dependent physicochemical properties and are a promising class of nanomaterials. As a consequence, for the rationalization of their synthesis and for the design of new clusters with tailored properties, a precise characterization of their composition and structure at the atomic level is required. We report a combined ion mobility-mass spectrometry approach with density functional theory (DFT) calculations for determination of the structural and optical properties of ultra-small gold nanoclusters protected by thioglycolic acid (TGA) as ligand molecules, Au₁₀(TGA)₁₀. Collision cross-section (CCS) measurements are reported for two charge states. DFT optimized geometrical structures are used to compute CCSs. The comparison of the experimentally- and theoretically-determined CCSs allows concluding that such nanoclusters have catenane structures. Full article

A series of a new type of tetracyclic carbazolequinones incorporating a carbonyl group at the ortho position relative to the quinone moiety was synthesized and analyzed by tandem electrospray ionization mass spectrometry (ESI/MS-MS), using Collision-Induced Dissociation (CID) to dissociate the protonated species. Theoretical parameters such as molecular electrostatic potential (MEP), local Fukui functions and local Parr function for electrophilic attack as well as proton affinity (PA) and gas phase basicity (GB), were used to explain the preferred protonation sites. Transition states of some main fragmentation routes were obtained and the energies calculated at density functional theory (DFT) B3LYP level were compared with the obtained by ab initio quadratic configuration interaction with single and double excitation (QCISD). The results are in accordance with the observed distribution of ions. The nature of the substituents in the aromatic ring has a notable impact on the fragmentation routes of the molecules. Full article

Factors affecting the kinetic isotope effects (KIEs) of the gas-phase S_N2 reactions and their temperature dependence have been analyzed using the ion-molecule collision theory and the transition state theory (TST). The quantum-mechanical tunneling effects were also considered using the canonical variational theory with small curvature tunneling (CVT/SCT). We have benchmarked a few ab initio and density functional theory (DFT) methods for their performance in predicting the deuterium KIEs against eleven experimental values. The results showed that the MP2/aug-cc-pVDZ method gave the most accurate prediction overall. The slight inverse deuterium KIEs usually observed for the gas-phase S_N2 reactions at room temperature were due to the balance of the normal rotational contribution and the significant inverse vibrational contribution. Since the vibrational contribution is a sensitive function of temperature while the rotation contribution is temperature independent, the KIEs are thus also temperature dependent. For S_N2 reactions with appreciable barrier heights, the tunneling effects were predicted to contribute significantly both to the rate constants and to the carbon-13, and carbon-14 KIEs, which suggested important carbon atom tunneling at and below room temperature. Full article