Negative Formation Research Articles

Large Negative-Ion Formation in Grazing Scattering of Neutral Carbon Atoms from a CsI(100) Surface

Large Negative-Ion Formation in Grazing Scattering of Neutral Carbon Atoms from a CsI(100) Surface

SF6 Negative Ion Formation in Charge Transfer Experiments.

In the present work, we report an update and extension of the previous ion-pair formation study of Hubers, M.M.; Los, J. Chem. Phys.1975, 10, 235-259, noting new fragment anions from time-of-flight mass spectrometry. The branching ratios obtained from the negative ions formed in K + SF6 collisions, in a wide energy range from 10.7 up to 213.1 eV in the centre-of-mass frame, show that the main anion is assigned to SF5- and contributing to more than 70% of the total ion yield, followed by the non-dissociated parent anion SF6- and F-. Other less intense anions amounting to <20% are assigned to SF3- and F2-, while a trace contribution at 32u is tentatively assigned to S- formation, although the rather complex intramolecular energy redistribution within the temporary negative ion is formed during the collision. An energy loss spectrum of potassium cation post-collision is recorded showing features that have been assigned with the help of theoretical calculations. Quantum chemical calculations for the lowest-lying unoccupied molecular orbitals in the presence of a potassium atom are performed to support the experimental findings. Apart from the role of the different resonances participating in the formation of different anions, the role of higher-lying electronic-excited states of Rydberg character are noted.

Low-Energy Electron Interactions with Methyl-p-benzoquinone: A Study of Negative Ion Formation.

Methyl-p-benzoquinone (MpBQ, CH3C6H3(=O)2) is a prototypical molecule in the study of quinones, which are compounds of relevance in biology and several redox reactions. Understanding the electron attachment properties of MpBQ and its ability to form anions is crucial in elucidating its role in these reactions. In this study, we investigate electron attachment to MpBQ employing a crossed electron-molecular beam experiment in the electron energy range of approximately 0 to 12 eV, as well as theoretical approaches using quantum chemical and electron scattering calculations. Six anionic species were identified: C7H6O2 -, C7H5O2 -, C6H5O-, C4HO-, C2H2 -, and O-. The parent anion is formed most efficiently, with large cross sections, through two resonances at electron energies between 1 and 2 eV. Potential reaction pathways for all negative ions observed are explored, and the experimental appearance energies are compared with calculated thermochemical thresholds. Although exhibiting similar electron attachment properties to pBQ, MpBQ's additional methyl group introduces entirely new dissociative reactions, while quenching others, underscoring its distinctive chemical behavior.

Robust and versatile assembly for emitter positioning, observation, and heating in atmospheric pressure field desorption mass spectrometry.

Atmospheric pressure field desorption (APFD) mass spectrometry (MS) has recently been introduced as a new variant of field desorption (FD) mass spectrometry. The development aimed at providing the basic characteristics of FD-MS in combination with instruments equipped with an atmospheric pressure (AP) interface. Hitherto, APFD has been demonstrated to yield both positive and negative even electron ions of highly polar or ionic compounds as well as to enable the generation of positive molecular ions, M+•, of polycyclic aromatic compounds. The prototype setup for APFD was based on a nano-electrospray ionization (nanoESI) source slightly modified to allow for emitter positioning in front of the AP interface of a Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer. The entrance electrode of the interface was set to negative or positive high voltage with respect to the emitter at ground potential, thereby permitting the formation of positive or negative ions, respectively. This work describes a custom-built device for quicker and more reproducible sample loading on and positioning of field emitters at the entrance electrode of the atmospheric pressure interface of a mass spectrometer. In addition, the device provides means for observation of the emitter during operation and for resistive emitter heating as employed in traditional FD-MS. Emitter heating both speeds up the desorption of the analytes and allows for the desorption/ionization of analytes of higher molecular weight than without emitter heating. In some cases, the signal-to-noise ratio of APFD mass spectra is improved due to higher ion currents effected by compressing the entire process into shorter periods of spectral acquisition. The new setup enables robust and reliable operation in APFD-MS. Moreover, it has been designed as to allow for use on a range of instruments as it can either be used on an FT-ICR mass spectrometer or in combination with a trapped ion mobility-quadrupole-time-of-flight (TIMS-Q-TOF) instrument.

Revisitation of reactive direct current magnetron sputtering discharge: Investigation of Mg–CF4, Mg–O2, and Ti–O2 discharges by probe measurements

The reactive direct current (DC) magnetron sputtering discharges of Mg–CF4, Mg–O2, and Ti–O2 were investigated using probe measurements as a function of reactive gas flow ratio. The emission spectroscopy, which was conducted before the probe measurements, demonstrates that all the three DC discharges transit from nonreactive to reactive discharge mode with increasing reactive gas flow ratio. The probe measurements show that the plasma potentials of the Mg–O2 and Ti–O2 DC discharges slightly increase or remain almost constant with increasing reactive gas flow ratio, whereas that of the Mg–CF4 DC discharge drastically decreases at the mode transition. For the same change in reactive gas flow ratio, the discharge voltage of the Mg–CF4 DC discharge slightly increases and that of the Mg–O2 DC discharge drastically increases at the mode transition, whereas that of the Ti–O2 DC discharge slightly decreases at the mode transition. The changes in the cathode sheath potential difference at the mode transition differ between the Mg–CF4 and Ti–O2 DC discharges and the Mg–O2 DC discharge because of the difference in the probability of secondary electron emission at the cathode surface; furthermore, the changes in the anode sheath potential difference at the mode transition differ between the Mg–CF4 DC discharge and the Mg–O2 and Ti–O2 DC discharges because of the difference in the probability of negative-ion formation in the plasma bulk. The most informative results obtained in this study were the differences in the potential differences at the cathode and anode sheaths among the Mg–CF4, Mg–O2, and Ti–O2 DC discharges. They well demonstrated the effects of the change in secondary-emitted species at the cathode surface and the change in reactive gas concentration in the plasma on the potential configuration.

Formation of negative ions from cobalt tricarbonyl nitrosyl Co(CO)3NO clusters.

Electron attachment and corresponding dissociative electron attachment (DEA) to cobalt tricarbonyl nitrosyl (Co(CO)3NO) clusters have been studied by co-expansion with Ar gas into a high vacuum. A monochromatic electron beam was utilized to generate negative ions and the resulting reaction products were identified using mass spectrometry. The ion fragments corresponding to Co(CO)3NO monomers closely resemble results from earlier gas phase experiments and studies conducted on Co(CO)3NO in He nanodroplets. However, contrary to the gas phase or He nanodroplet ion yields, a resonance structure comprising several peaks at energies above ∼4 eV was observed both in the case of molecular clusters [Co(CO)3NO]n- (with n = 1, 2, 3) and clusters comprising DEA fragments. Additionally, the ion yields of numerous other clusters such as ions without nitrosyl ([Co(CO)4]-, [Co2(CO)5]-), clusters consisting of two fragments such as ([Co2(CO)NO]-, [Co2(CO)(NO)2]-, [Co2(CO)2NO]-, [Co2(CO)2(NO)2]-, [Co3(CO)(NO)3]-, [Co3(CO)8(NO)3]-, [Co3(CO)(NO)2]-, [Co3(CO)3(NO)2]-, and [Co3(CO)5(NO)2]-) were recorded. Moreover, NO bond dissociation was confirmed with the [Co(CO)2N]-ion and with N- or O-retaining cluster ions, such as [Co2(CO)(NO)N]-, [Co2(CO)2(NO)N]-, [Co3(CO)2(NO)N]-, [Co3(CO)3(NO)N]- and [Co3(CO)(NO)2N]-, or [Co2(CO)2O]-, [Co2(CO)3O]-, [Co3(CO)3O]-, [Co3(CO)4O]-and [Co3(CO)2(NO)O]- respectively.

Molecular ionization potentials of triglycerides and mechanism analysis of streamer discharge in vegetable insulating oil

With the enhancement of social awareness of environmental protection, scholars have gradually began to focus their research on vegetable-oil-based insulating fluid. In this work, we calculated the ionization potential of triglyceride molecules in vegetable oil (VO), analyzed the mechanism of charge generation, and explained the cause of fast streamer discharge in VO based on the distribution characteristics of ionization potential. Some interesting results were obtained. The position of CC on the triglyceride branch chain can affect the ionization potential of triglycerides. Specially, the CC at the Sn-2 position can significantly reduce the ionization potential of glycerol molecules. The ionization of unsaturated triglycerides is mainly caused by the electron loss of carbon atoms in the CC double bond; the formation of negative ions mainly rely on ester groups and their nearby atoms to capture electrons. In VO, low ionization potential molecules are predominantly present, and their presence results in a lower breakdown voltage and easy formation of the fast streamer discharge. We anticipate that our research can provide theoretical support for the application research of vegetable insulating fluid.

Electron Capture Dissociation by Triclocarban Molecules

The formation and decay of molecular negative ions (MNIs) formed during resonant scattering of electrons by triclocarban molecules were studied by dissoiative electron attachment (DEA) spectroscopy. The most intense channel observed in the mass spectrum are MNIs formed at the thermal energy of trapped electrons with a lifetime relative to electron autodetachment of ~2800 μs. The experimental results were interpreted using CAM-B3LYP/6-311+G(d,p) calculations, which made it possible to reveal a number of important features of the geometry of molecular and fragment negative ions. Namely, the most stable geometry of MNIs is such that one of the chlorine atoms is coordinated with two hydrogen atoms of the structural element of urea. The charge on the chlorine atom is ~–0.7e–, which allows us to interpret this state as the result of the “roaming” of the chlorine atom in the MNI. According to calculations, the adiabatic electron affinity (EAa) of the triclocarban molecule is 1.66 eV. Evaluation of EAa in a simple Arrhenius approximation gives 1.2–1.4 eV. An analysis of the potential of the appearance of fragment ions with a C6H3Cl2NH2 structure made it possible to discover the noncovalent structure of these pseudo-MNIs, in which the chlorine atom is coordinated with two hydrogen atoms of the amino group.

Electron Collisions with Multielectron Atoms and Fullerene Molecules: Strong Polarisation Effects

Regge pole-calculated low-energy electron elastic total cross sections for multielectron atoms/fullerenes are characterised by ground, metastable and excited negative-ion formation, shape resonances and Ramsauer-Townsend minima. In this article, we demonstrate through the total cross sections for Eu, Au and At atoms and C60 fullerene the sensitivity of stable negative-ion formation to the crucial core-polarisation potential. The energy positions of the dramatically sharp resonances corresponding to the binding energies of the formed anions during the collisions agree excellently with the measured electron affinities of the atoms and C60. The sensitivity of Ramsauer-Townsend minima and shape resonances to the electronic structure and dynamics of Bk and Cf permits their first ever use as novel validation of the experimental observation that Cf is indeed a transitional element in the actinide series. Their electron affinities are also calculated.

Fast and cold negative ion and neutral atom beams from a water spray

High-power lasers are routinely used to generate energetic positively charged ions, and this paper reports on the observation of negative ions in these experiments. A large number of negative ions and neutral atoms at MeV energies was obtained from the interaction of a high intensity laser pulse with a water spray along with positive ions [Abicht et al., Appl. Phys. Lett. 103, 253501 (2013)]. Beams of negative ions and neutral atoms have the same properties as beams of positive ions. However, the mechanism of negative ion formation and acceleration is still under discussion. In order to gain more information about physics of generation negative ions and neutrals, we present a new experiment where all species, positive, negative ions, and neutrals, are spatially separated, and the electron capture and loss of each in water spray is evaluated. The formation of negative ions and neutral atoms of hydrogen and carbon with energies up to 140 keV and 1.2 MeV, respectively, is confirmed. It is suggested that the electrification of spray droplets plays a decisive role in these charge-exchange processes.

Acenaphto[1,2-k]fluoranthene: Role of the Carbon Framework Transformation for Tuning Electronic Properties

Acenaphtho[1,2-k]fluoranthene (1) is synthesized via tandem cyclization during the dehydrofluorination of 1,4-di(1-naphthyl)-2,5-difluorobenzene (2) on activated γ-Al2O3. Presence of residual hydroxyl groups in alumina reduce the yield of target product 1 because of the side hydrolysis of fluoroarenes with the formation a product of partial cyclization, 9-(1-naphthyl)fluoranthen-8-ol (1b). The formation of negative ions (NI) of compounds 1 and 2 in the gas phase is studied by means of dissociative electron attachment (DEA) spectroscopy. Long-lived molecular NIs 1 and 2 are registered at the thermal energies of electrons, and patterns of their fragmentation are established. The adiabatic electron affinities of compounds 1 and 2 are estimated in the Arrhenius approximation and equal 1.17 ± 0.12 and 0.71 ± 0.07 eV, respectively, which agree with data from quantum chemical modeling at the level of the density functional theory (DFT). Electronic transitions for compounds 1 and 2 are studied via optical absorption and fluorescence spectroscopy. Fluorescence quantum yields are measured, and the resulting data are interpreted according to the time dependent DFT. The electrochemical properties of compounds 1, 1b, and 2 are studied via cyclic voltamperometry, and the levels of boundary molecular orbitals are estimated on the basis of their formal potentials of reduction and oxidation.

Acenaphto[1,2-k]fluoranthene: Role of the Carbon Framework Transformation for Tuning Electronic Properties

Acenaphtho[1,2-k]fluoranthene (1) is synthesized via tandem cyclization during the dehydrofluorination of 1,4-di(1-naphthyl)-2,5-difluorobenzene (2) on activated γ-Al2O3. Presence of residual hydroxyl groups in alumina reduce the yield of target product 1 because of the side hydrolysis of fluoroarenes with the formation a product of partial cyclization, 9-(1-naphthyl)fluoranthen-8-ol (1b). The formation of negative ions (NI) of compounds 1 and 2 in the gas phase is studied by means of dissociative electron attachment (DEA) spectroscopy. Long-lived molecular NIs 1 and 2 are registered at the thermal energies of electrons, and patterns of their fragmentation are established. The adiabatic electron affinities of compounds 1 and 2 are estimated in the Arrhenius approximation and equal 1.17 ± 0.12 and 0.71 ± 0.07 eV, respectively, which agree with data from quantum chemical modeling at the level of the density functional theory (DFT). Electronic transitions for compounds 1 and 2 are studied via optical absorption and fluorescence spectroscopy. Fluorescence quantum yields are measured, and the resulting data are interpreted according to the time dependent DFT. The electrochemical properties of compounds 1, 1b, and 2 are studied via cyclic voltamperometry, and the levels of boundary molecular orbitals are estimated on the basis of their formal potentials of reduction and oxidation.

Isotope Effect in D2O Negative Ion Formation in Electron Transfer Experiments: DO-D Bond Dissociation Energy.

H2O/D2O negative ion time-of-flight mass spectra from electron transfer processes at different collision energies with neutral potassium yield OH-/OD-, O-, and H-/D-. The branching ratios show a relevant energy dependence with an important isotope effect in D2O. Electronic state spectroscopy of water has been further investigated by recording potassium cation energy loss spectra in the forward scattering direction at an impact energy of 205 eV (lab frame), with quantum chemical calculations for the lowest-lying unoccupied molecular orbitals in the presence of a potassium atom supporting most of the experimental findings. The DO-D bond dissociation energy has been determined for the first time to be 5.41 ± 0.10 eV. The collision dynamics revealed the character of the singly excited (1b2-1) molecular orbital and doubly excited states in such K-H2O and K-D2O collisions.

Rigorous Negative Ion Binding Energies in Low-Energy Electron Elastic Collisions with Heavy Multi-Electron Atoms and Fullerene Molecules: Validation of Electron Affinities

Dramatically sharp resonances manifesting stable negative ion formation characterize Regge pole-calculated low-energy electron elastic total cross sections (TCSs) of heavy multi-electron systems. The novelty of the Regge pole analysis is in the extraction of rigorous and unambiguous negative ion binding energies (BEs), corresponding to the measured electron affinities (EAs) of the investigated multi-electron systems. The measured EAs have engendered the crucial question: is the EA of multi-electron atoms and fullerene molecules identified with the BE of the attached electron in the ground, metastable or excited state of the formed negative ion during a collision? Inconsistencies in the meaning of the measured EAs are elucidated and new EA values for Bk, Cf, Fm, and Lr are presented.

Lignin-grafted quaternary ammonium phosphate with temperature and pH responsive behavior for improved enzymatic hydrolysis and cellulase recovery

The cost of lignocellulosic enzymatic hydrolysis was reduced by enhancing enzymatic hydrolysis and recycling cellulase. Lignin-grafted quaternary ammonium phosphate (LQAP) with sensitive temperature and pH response, was obtained by grafting quaternary ammonium phosphate (QAP) onto enzymatic hydrolysis lignin (EHL). LQAP dissolved under the hydrolysis condition (pH 5.0, 50 °C) and enhanced the hydrolysis. After hydrolysis, LQAP and cellulase co-precipitated by the hydrophobic binding and electrostatic attraction, when lowering pH to 3.2, and cooling to 25 °C. LQAP had significant performances of pH-UCST response, enzymatic hydrolysis enhancement and cellulase recovery at the same time. When 3.0 g/L LQAP-100 was added to the system of corncob residue, SED@48 h increased from 62.6 % to 84.4 %, and 50 % of amount of cellulase was saved. Precipitation of LQAP at low temperature was mainly attributed to the salt formation of positive and negative ions in QAP; LQAP enhanced the hydrolysis for its ability to decrease the ineffective adsorption of cellulase by forming a hydration film on lignin and through the electrostatic repulsion. In this work, a lignin amphoteric surfactant with temperature response, was used to enhance hydrolysis and recover cellulase. This work will provide a new idea for reducing the cost of lignocellulose-based sugar platform technology, and high-value utilization of industrial lignin.

Laser-Induced Ion Formation and Electron Emission from a Nanostructured Gold Surface at Laser Fluence below the Threshold for Plasma Formation.

The laser formation of positive and negative ions on a nanostructured metal surface is observed at laser fluence below the plasma formation threshold. The laser radiation energy dependences of the yield of positive and negative Au ions and charged clusters as well as electrons from the laser-induced nanostructures on the surface of gold are obtained at laser fluence below the plasma formation threshold using a pulsed laser with a wavelength of 355 nm and a pulse duration of 0.37 ns. It is shown that the ratio of the signals of positive and negative ions is constant over the entire range of the laser radiation energies, while the ion signal dependence on the laser radiation energy is described by a power function with an exponent of 9. The role of gold nanoparticles with a size of less than 5 nm in the formation of Au ions and charged Au clusters is discussed.

From meniscus formation to accelerated H− beam: coupling of 3D-PIC and ion-optics simulations

The ITER NBI is based on negative hydrogen ions extracted from caesiated ion sources. The 3D particle-in-cell Monte Carlo collision code Orsay negative ion extraction (ONIX) models the beamlet formation of negative ions in such sources where surface production plays an important role. A coupling scheme between ONIX and the ion-optics code ion beam simulator (IBSimu) has been developed and compared to other particle simulation approaches. This extends the computational domain such that the complete grid system can be included while only marginally increasing the computational cost. The properties of the accelerated ONIX beamlet are studied and compared to standalone IBSimu calculations, which are based on a simplified plasma model. The comparison provides insight about the effect of approximations made in ion-optics codes, which were also used to design the ITER NBI grid systems. ONIX volume and surface produced negative ions have a different angular distribution in the accelerated beamlet. The ONIX volume produced particles have a similar core divergence compared to standalone IBSimu calculations, but there is more halo in the IBSimu angular distribution. In the ONIX simulations, a Debye sheath is formed between the plasma and the grid, which repels negatively charged particles. The sheath decreases the extracted current density at the edge of the aperture for volume produced ions. Contrarily, surface produced particles are directly extracted near the edge of the aperture. Particles extracted near the edge of the aperture are highly divergent at the end of the grid system, independent of their initial angle. To summarize, the presence of the plasma sheath around the apertures in the plasma grid as calculated by ONIX decreases the halo from volume produced particles compared to standalone IBSimu.

Dissociative electron attachment to p-fluoranil and p-chloranil.

The processes of formation and decay of negative molecular ions (NMI) of p-fluoranil [2,3,5,6-tetrafluoro-1,4-benzoquinone (FA)] and p-chloranil [2,3,5,6-tetrachloro-1,4-benzoquinone (CA)] in the gas phase were investigated. In both cases, long-lived NMIs were found in two resonances, at thermal electron energies and in the region of 0.8-0.9eV, with lifetimes relative to electron ejection of τa ∼ 600 µs. The dissociation of molecular NIs with the formation of fragment ions [M-COF2]-, [M-CO]-, and Cl- proceeds at microsecond times, which is confirmed by the registration of the corresponding metastable ions. It is shown that the dependence of the lifetime of MNIs on the electron energy can be explained by the presence of a transition state at an energy of ∼0.5eV.

Implementation of Islamic Education Concept in Ethnochemistry

The concept of Islamic education requires more than just a theoretical understanding. It concentrates only on Islamic studies because of the difficulties in using a chemical perspective to understand the concepts. Therefore, this study aims to implement an Islamic education concept in ethnochemistry using Sasak traditional wisdom. It uses qualitative methodologies such as observation, in-depth interviews, documentation, and curriculum analysis to obtain data. The results show that ethnochemistry based on the local wisdom of the Sasak tribe has a strong relationship with the Islamic education concept, especially in the merarik (marriage) ceremony. A fundamental part of Islamic education is a belief in the need for mutual respect, cooperation, open debate, and consensus, reciprocal give and take, collaboration, and the necessity for stability. These ideas are also very relevant to the chemical bond theory, which includes concepts such as electron stability, electron configuration, positive and negative ion formation, as well as chemical bond formation. Therefore, ethnochemistry based on Sasak local wisdom can be considered relevant to the Islamic education concept. Acknowledging intellectually and ethically intelligent students is essential to achieving national education goals.

Formation of Temporary Negative Ions and Their Subsequent Fragmentation upon Electron Attachment to CoQ0 and CoQ0H2

AbstractThe front cover artwork is provided by Prof. Stephan Denifl's group at the University of Innsbruck, Austria, in collaboration with Prof. Filipe Ferreira da Silva's group at NOVA University Lisbon, Portugal, and Prof. Dr. Márcio Varella's group at University of São Paulo, Brazil, as well as with Prof. Dr. Martin Beyer and Prof. Dr. Milan Ončak also at the University of Innsbruck, Austria. The image shows the main fragmentation pathways of both coenzyme Q0 (CoQ0) and CoQ0H2 upon electron attachment in the gas phase. Read the full text of the Research Article at 10.1002/cphc.202100834.