Electron Attachment Reactions Research Articles

Simulation on the effect of oxygen concentration on the positive secondary streamer generated in oxygen-rich nitrogen–oxygen mixtures under atmospheric pressure

In this study, we investigated the effect of various O2 concentrations, from 20% to 90%, in nitrogen–oxygen ( N2/O2 ) mixtures on the characteristics of secondary streamers. As oxygen molecules have different molecular characteristics from nitrogen molecules in terms of ionisation threshold and electron attachment property, streamer discharges generated under various nitrogen–oxygen ratios may exhibit differing characteristics such as electron density, electric field, and radical formation. We focused on the changes in these parameters in secondary streamers using simulations. Simulations were first performed under the same conditions as those in previous experiments to compare the results of the ozone production, discharge current, and discharge emission characteristics. To compare the ozone production characteristics, simulated O radicals–the precursor of ozone–were used in the simulation for simplicity. This comparison showed that, although the absolute values of each parameter were different, the simulation exhibited a similar trend in the case of the experimentally obtained oxygen concentration dependence. After the validity of the simulation was verified to some extent via a comparison with the experiment, the results obtained from the simulation were analysed in detail. The results showed that, although the electric field strength in the secondary streamer did not change much as the oxygen concentration increased, the decrease rate of the electron density was greatly accelerated by the electron attachment reaction of oxygen. As a result, many of the electrons had already dissipate during the development of the primary streamer, and few electrons remained when the secondary streamer was formed. This effect suggests that the ratio of the amount of O radicals produced in the primary streamer to that produced in the secondary streamer changes as the oxygen concentration changes.

Experimental study of the influence of O2 content on electrical and optical characteristics of He/CF4 APPJ

CF4 is an important source of reactive F-containing species (RFS) so that it is used to mix with inert gas as the working gas of atmospheric pressure plasma jet (APPJ) for material surface fluoridation modification. The addition of a small amount of O2 can increase the density of RFS in He/CF4 APPJ. Therefore, the hydrodynamic, electrical and optical properties of He/CF4/O2 APPJ interacting with the dielectric are experimentally investigated in this paper. Meanwhile, the influence of the excitation source on plasma discharge is discussed in detail and the internal mechanism of the experimental phenomenon in this paper is analyzed using the simulation results based on the model established in the previous paper. It is found that the addition of a small amount of O2 can increase the intensity and accelerate the axial propagation speed of He/CF4 APPJ due to the low ionization energy of O2 and the increase of the Penning ionization between metastable He and O2. With the increase of O2 content, the stability of the discharge is gradually enhanced due to the electron attachment reaction of O2 and the position of the primary current pulse in each half voltage cycle gradually approaches the position of the peak voltage because the increase in O2 content raises the breakdown threshold in dielectric barrier discharge region. In the presence of downstream dielectric, the addition of 0.1%O2 does not significantly change the radial development radius of APPJ due to the higher electron attachment rate and electron collision excitation loss power. The discharge pulse intensity is generally reduced compared to the absence of dielectric and the glow discharge in the strict sense no longer exists. The continuous spectrum intensity of RFS increases with the addition of a small amount of O2 while decreases significantly when O2 content is too high.

Effect of CF4 concentration on the discharge dynamics and reactive species distribution of atmospheric nanosecond pulsed He plasma jet

Based on a two dimensional self-consistent model, the effect of different CF4 concentrations on the discharge dynamics characteristics, F-containing species distribution and the distribution of the axial and radial ionization rates of He atmospheric pressure plasma jet (APPJ) has been investigated. In addition, the accuracy of the simulation is verified by comparing the experimental results. The ionization rate of He APPJ enhances with the increase of CF4 from 0% to 2% because of the Penning ionization of CF4 with metastable He while decreases in the case of 3% CF4 owing to the electronegativity and the electron excitation energy loss of CF4. The increase of CF4 concentration and the decrease of the electron density leads to the decrease of CF4 + density at 3% CF4. CF3 + density is determined by the Penning ionization rate of CF4 and the reaction rate of He+ + CF4 → CF3 + + F + He. As CF4 concentration increases from 2% to 3%, the decrease of metastable He and He+ concentration results in the significant decrease of CF3 + density. The densities of CF3 − and F− keep increasing from 1% to 3% CF4 due to the effect of the electron attachment reaction of CF4. With the addition of CF4, the ionization reaction of CF4 is gradually playing the major role in the streamer head, the Penning ionization of CF4 is the main source of electron ionization inside the jet and dominates in the formation of ionization wave tail. As the concentration of CF4 increases from 0% to 2%, the electron impact ionization rates of He and CF4 near the axis increase, resulting in the more uniform radial ionization rate distribution of He + 2% CF4 APPJ.

Excited State Nonadiabatic Molecular Dynamics of Hot Electron Addition to Water Clusters in the Ultrafast Femtosecond Regime

Dissociative electron attachment (DEA) reactions of water result in the production of hydrogen atoms and hydroxide anions. This has been studied for a long time and is relatively slow in liquid water for thermalized hydrated electrons but much faster with a higher-energy electron. Here, we probe the nonadiabatic molecular dynamics after the addition of a hot electron (6-7 eV) to a neutral water cluster (H2O)n, where n = 2-12, considering the 0-100 fs time scale using the fewest switches surface hopping method, in conjunction with ab initio molecular dynamics and the Tamm-Dancoff approximation density functional theory method. The nonadiabatic DEA occurs within 10-60 fs, and with high probability, giving H + OH- above an energy threshold. This is faster than time scales estimated previously for autoionization or adiabatic DEA. The change in threshold energy with cluster size is modest, ranging from 6.6 to 6.9 eV. Dissociation on a femtosecond time scale is consistent with pulsed radiolysis experiments.

Effects of oxygen concentration on streamer propagation and ozone production in a single-filament streamer discharge at atmospheric pressure

Limited research has been conducted on the formation mechanism of chemically active species in streamer discharges with respect to the oxygen concentration, which is critical to various applications such as ozone generation, air purification, and plasma-assisted combustion, among others. Herein, the oxygen concentration in an N2/O2 gas atmosphere is varied from 1% to 99% under atmospheric pressure and room temperature to investigate changes in the characteristics of streamer discharge propagation and generation of chemically active species. As the oxygen concentration increases from 10% to 90%, the decay rate of the discharge current, propagation velocity of the primary streamer, and ozone production efficiency increase. These phenomena are qualitatively explained by the electron attachment reaction to oxygen molecules and changes in the electron energy distribution function caused by the change in the oxygen concentration. However, the amount of discharge emission from N2(C) cannot be explained by changes in the fraction of electron energy lost in excitation of N2(C) and its quantum yield, implying that changes in the production of N2(C) in the primary and secondary streamers must be considered in a spatiotemporal manner. This study demonstrates that the ozone and N2(C) production characteristics in streamer discharges vary nonlinearly with respect to the oxygen concentration.

Plasma Electrochemistry: Redox Reactions in Gases

Electrochemistry underpins numerous commercially important processes ranging from energy generation to sensors and coating deposition. A common and –so far– essential feature of all these processes involve a redox active species dissolved in a solvent which serves to allow charge exchange between electrodes. Rather than being inert, the solvent is without exception redox-active at extreme potentials and thus restrict the breadth of observable reactions to a narrow potential window of approx. -2.5 to +2.5 V vs. NHE. Gaseous electrolytes have typically been ignored due to their feeble electrical conductivity. However, recently with the advent of new accessible approaches to form stable plasmas, these electrically conducting gases are attracting some significant interest and are now being investigated as exotic electrochemical environments. The scope of this work is to apply the well-healed cornerstones of electrochemistry developed almost exclusively in liquids, to the new context of gaseous plasma.The defining property of plasmas is presence of free electrons; because of this they may be considered as both electrodes or electrolytes1&2. We describe results supporting both modes. As electrodes, we show that metal oxides on surfaces may be reduced to zero valent metals using a helium atmospheric plasma jet.3&4 We show that free electrons do indeed reduce a copper oxide film, which may be carefully controlled by surface bias.5 A gaseous flame doped with electroactive species may be considered as electrolytes. Using a three-electrode system6, we may measure unique voltammograms for a series of small organic molecules and amino acids.7 Except for leucine and isoleucine, all were distinguishable. The reduction signatures originate from specific electron attachment reactions of radicals formed via incomplete combustion and fragmentation of the parent molecules. In this case without a solvent we have an extended potential window and our voltammograms extend between 0 and -10 V, which gives unprecedented access to chemistry not previously accessible in liquids. Moreover, mass transport properties are far better than in liquids, as such the fluxes of electroactive species to the electrode a much greater. References Rumbach, P.; Bartels, D. M.; Sankaran, R. M.; Go, D. B., The solvation of electrons by an atmospheric-pressure plasma. Nature Communications 2016, 6, 7248.Elahi, A.; Fowowe, T.; Caruana, D. J., Dynamic Electrochemistry in Flame Plasma Electrolyte. Angewandte Chemie-International Edition 2012, 51 (26), 6350-6355.Sener, M. E., Quesada Cabrera, R., Parkin, I.P., Caruana, D. J., Facile formation of black titania films using an atmospheric-pressure plasma jet, Green Chemistry 2022, 24, 2499-2505.Sener, M. E., Palgrave, R., Quesada Cabrera, R., Caruana, D. J., Patterning of Metal Oxide thin Films using H2/He Atmospheric Pressure Plasma Jet. Green Chemistry 2020, 22, 1406-1413.Sener, M. E.; Caruana, D. J., Modulation of copper(I) oxide reduction/oxidation in atmospheric pressure plasma jet. Electrochemistry Communications 2018, 95, 38-42.Fowowe, T.; Hadzifejzovic, E.; Hu, J. P.; Foord, J. S.; Caruana, D. J., Plasma Electrochemistry: Development of a Reference Electrode Material for High Temperature Plasma. Advanced Materials 2012, 24 (47), 6305-6309.Calleja, M.; Elahi, A.; Caruana, D. J., Gas phase electrochemical analysis of amino acids and their fragments. Communications Chemistry 2018, 1, 48.

Numerical study of the influence of O2 admixture on the propagation and F-containing species distribution of He/CF4 atmospheric pressure plasma jet

O2 impurity in the working gas of an He/CF4 atmospheric pressure plasma jet (APPJ) can affect the discharge dynamics and the density of reactive species. Therefore, a two-dimensional (2D) fluid model is built in order to explore the influence of an O2 admixture on the propagation and F-containing species distribution of He/CF4 APPJ. The addition of 0.1% O2 accelerates the ionization rates of APPJ due to the increase of Penning ionization reactions of O2, resulting in the increases of axial speed and F-containing reactive species (CF4+, CF3+, CF2+, CF+, F+, CF3, F, CF3−) when APPJ approaches the dielectric surface. The addition of O2 has the inhibitory effect on the rise of some F-containing reactive species (CF3+ and F). As O2 concentration increases to 2%, the concentration of F-containing reactive species shows a downward trend due to the increase of excitation energy loss and an electron attachment reaction of O2. Different from the axial speed, the radial speed decreases continuously with the increase of O2 because of the high O2 concentration on the dielectric surface when APPJ propagates radially. This also results in a reduced distribution of reactive species fluxes. The excitation energy loss and electronegativity of O2 and CF4 in the case of He + 0.5% CF4 + 0.5% O2 have been presented in this paper. It is discovered that excitation energy loss of O2 is stronger than that of CF4, but the electronegativity of CF4 is stronger than that of O2.

Effect of CF4 ratio on the interaction of atmospheric nanosecond pulsed He plasma jet with a dielectric material

In this paper, a two dimensional (2D) axisymmetric fluid model is built to study the effect of the ratio of CF4 admixture on the plasma dynamics and F-containing species concentration in He atmospheric pressure plasma jet. The steady mole fraction distribution of He and CF4 is first studied, which presents that the mole fractions of CF4 show peaks at 5 mm from the symmetry axis on the dielectric surface due to the dual influences of the boundary layer effect and air mixing. The CF4 admixture enhances the propagation speed of ionization wave, and the axial velocity reaches the peak value in the case of He + 1.5% CF4. The conversion from the ring-shaped plasma–surface interaction to a solid-disk one results from the addition of CF4. The Penning ionization of CF4 accelerates the plasma jet propagation within 1.5% CF4. However, the excitation energy loss and electron attachment caused by the addition of CF4 also quench the propagation of plasma jet, which become obvious in the case of 2% CF4. F-containing groups (CF4+, CF3+, CF3−, F−, CF3, and F), mainly produced by the Penning ionization reaction, electron attachment reaction, and He+ + CF4 → He + CF3+ + F, also show peaks for He + 1.5% CF4. On the dielectric surface, as the radial distance increases, the ratio of F-containing neutral species (CF3 and F) to O atom at 200 ns decreases due to the increase of O atom concentration and then increases at the streamer head because the surface flux of CF3 reaches the maximum value. The maximum surface flux radial distribution distance for ratio of F-containing species to O atom, CF3 and F appear in the case of 1.5% CF4.

(Invited) Plasma Electrochemistry: Plasmas Are so Much More Fun for Electrochemistry Than Liquids!

As electrochemists, we are interested in electron attachment and detachment processes. Traditionally, we control the availability of electrons via an electrically conducting solid and measure electron transfer across the solid/liquid interface. Of course, there are exceptions to this picture, e.g. liquid/liquid interfaces, but often liquids are involved to provide an electrolyte medium to support the chemical species. Gaseous electrolytes have typically been ignored due to their feeble electrical conductivity. However, recently with the advent of new accessible approaches to form stable plasmas, these electrically conducting gases are attracting some significant interest and are now being investigated as exotic electrochemical environments.The defining property of plasmas is presence of free electrons; because of this they may be considered as both electrodes or electrolytes1, 2. We describe results supporting both modes.As electrodes, we show that metal oxides on surfaces may be reduced to zero valent metals using a helium atmospheric plasma jet.3 We show that free electrons do indeed reduce a copper oxide film, which may be carefully controlled by surface bias.4 A gaseous flame doped with electroactive species may be considered as electrolytes. Using a three-electrode system5, we may measure unique voltammograms for a series of small organic molecules and amino acids.6 Except for leucine and isoleucine, all were distinguishable. The reduction signatures originate from specific electron attachment reactions of radicals formed via incomplete combustion and fragmentation of the parent molecules. In this case without a solvent we have an extended potential window and our voltammograms extend between 0 and -10 V, which gives unprecedented access to chemistry not previously accessible in liquids. Moreover, mass transport properties are far better than in liquids, as such the fluxes of electroactive species to the electrode a much greater. References Rumbach, P., Bartels, D.M., Sankaran, R.M. & Go, D.B. The solvation of electrons by an atmospheric-pressure plasma (vol 6, pg 7248, 2015). Nature Communications 7 (2016).Elahi, A., Fowowe, T. & Caruana, D.J. Dynamic Electrochemistry in Flame Plasma Electrolyte. Angewandte Chemie-International Edition 51, 6350-6355 (2012).Sener, M.E., Palgrave, R., Quesada Cabrera, R., Caruana, D.J.*, Patterning of Metal Oxide thin Films using H2/He Atmospheric Pressure Plasma Jet. Green Chemistry,22, 1406-1413 (2020).Sener, M.E. & Caruana, D.J. Modulation of copper(I) oxide reduction/oxidation in atmospheric pressure plasma jet. Electrochemistry Communications 95, 38-42 (2018).Fowowe, T., Hadzifejzovic, E., Hu, J.P., Foord, J.S. & Caruana, D.J. Plasma Electrochemistry: Development of a Reference Electrode Material for High Temperature Plasma. Advanced Materials 24, 6305-6309 (2012).Calleja, M., Elahi, A. & Caruana, D.J. Gas phase electrochemical analysis of amino acids and their fragments. Communications Chemistry 1, 48 (2018).

Thymidine and stavudine molecules in reactions with low-energy electrons

The negative ion formation and fragmentation processes in thymidine and stavudine were studied by means of resonant electron capture mass spectrometry in the electron energy range 0–14 eV. Stavudine is a nucleoside analog of thymidine, that differs from the latter by the presence of double bond in the deoxyribose moiety. In the energy range below 5 eV transient negative ions have been found to arise via shape resonances resulting in electron attachment into the empty π*-orbitals. The main fragmentation channels for molecular ions are the H-atom loss and N-glycosidic bond cleavage between sugar and a nucleobase moieties. The dissociative electron attachment cross sections for the fragment negative ions were measured. The structures for some observed anions and neutral counterparts were suggested basing on the thermochemical approach for dissociative reactions energy balance under the support of quantum chemical calculations. The processes of ion formation in thymidine were found to be similar to those revealed previously for deoxyuridine nucleoside. In contrast, very strong dissociative channel was found for stavudine yielding [M–R]– ions (where R is a sugar moiety) in the energy range <3 eV. The efficient fragmentation found for stavudine in the low energy electron attachment reactions may have implications for the design of nucleoside radiosensitizers for cancer therapy.

Perfluoro effect on the electronic excited states of para-benzoquinone revealed by experiment and theory

We report a comprehensive study on the electronic excited states of tetrafluoro-1,4-benzoquinone, through high-resolution vacuum ultraviolet photoabsorption spectroscopy and time-dependent density functional theory calculations performed within the nuclear ensemble approach. Absolute cross section values were experimentally determined in the 3.8-10.8 eV energy range. The present experimental results represent the highest resolution data yet reported for this molecule and reveal previously unresolved spectral structures. The interpretation of the results was made in close comparison with the available data for para-benzoquinone [Jones et al., J. Chem. Phys., 2017, 146, 184303]. While the dominant absorption features for both molecules arise from analogous π* ← π transitions, some remarkable differences have been identified. The perfluoro effect manifests in different ways: shifts in band positions and cross sections, appearance of features associated with excitations to σCF* orbitals, and spectrum broadening by quenching of either vibrational or Rydberg progressions. The level of agreement between experiment and theory is very satisfactory, yet that required the inclusion of nuclear quantum effects in the calculations. We have also discussed the role of temperature on the absorption spectrum, as well as the involvement of core-excited resonances in promoting dissociative electron attachment reactions in the 3-5 eV range.

5-Nitro-2,4-Dichloropyrimidine as an Universal Model for Low-Energy Electron Processes Relevant for Radiosensitization.

We report experimental results of low-energy electron interactions with 5-nitro-2,4-dichloropyrimidine isolated in the gas phase and hydrated in a cluster environment. The molecule exhibits a very rare combination of many so far hypothesized low-energy electron induced mechanisms, which may be responsible for synergism in concurrent chemo-radiation therapy of cancer. In contrast to many previous efforts to design an ideal radiosensitizer based on one mode of action, the present model molecule presents an alternative approach, where several modes of action are combined. With respect to the processes induced by the low-energy electrons, this is not a trivial task because of strong bond specificity of the dissociative electron attachment reaction, as it is discussed in the present paper. Unfortunately, low solubility and high toxicity of the molecule, as obtained from preliminary MTT assay tests, do not enable further studies of its activity in real biological systems but it can advantageously serve as a model or a base for rational design of radiosensitizers.

Shape Resonances and Elastic Cross Sections in Electron Scattering by CF3Br and CF3I.

Trifluoroiodomethane (CF3I) is one of the most appealing candidates for applications in plasma-based technologies in view of its many interesting advantages when compared to more standard gases such as trifluorobromomethane (CF3Br). Low-energy electrons are prone to decomposing these molecules into reactive species, and knowledge on the collision cross sections is fundamental for modeling transport and reactivity in plasma environments. Despite many studies on electron collisions with the abovementioned molecules, there are conflicting results on the assignment of shape resonances and on the magnitudes of total cross sections. Here, we try to clarify these aspects by performing ab initio electron scattering calculations. We found integral cross sections in fair agreement with the most recent measurements, in contrast to previous reports. For each molecule, we found a σCX* resonance (antibonding between the carbon and the heavy halogen) at 1 eV in CF3Br and at ∼0 eV in CF3I. Furthermore, there are three shape resonances of σCF* character; two are degenerate and account for a broad feature around 6 eV and the other one appears around 9.5 eV. We also discuss the possible role of the degenerate resonance in dissociative electron attachment reactions, as well as the impact of the heavy halogen on the cross sections and on the shape resonances.

Experimental observation of the effect of electron attachment and detachment reactions on the electron energy distribution in an inductive oxygen discharge

Electron energy distribution functions (EEDFs) are measured with varying radio-frequency (RF) power in an oxygen inductive discharge. At a pressure of 10 mTorr, the EEDF has a Maxwellian distribution, and the low-energy (1–5 eV) electron temperature, Te,low, monotonically decreases with RF power. However, at a pressure of 100 mTorr, Te,low increases at low RF power (80–150 W) and decreases at high RF power (150–300 W), and the EEDF has a Druyvesteyn-like distribution. These changes in Te,low are attributed to electron attachment and detachment reactions, which are the main creation and loss reactions of negative ions. To investigate this relationship between Te,low and collisional reactions, the reaction coefficients of several reactions are calculated, and the electronegativity (α) is measured with varying RF power. The EEDF is modified by electron attachment and detachment reactions, which lead to a change in Te,low; this modification of EEDF is supported by calculated reaction coefficients and measured α.

Numerical simulation on electric field intensity and reaction pathway in the He–O2 atmospheric pressure plasma jet

In this work, a two-dimensional fluid model of the needle-plane discharge plasma has been built to numerically investigate the spatio-temporal evolution characteristics of the electric field intensity and electric potential as well as generating and consuming reaction pathways of various oxygen species in a He–O2 atmospheric pressure plasma jet. Simulation results have indicated that the region of high electric field intensity moves in the direction of the plane electrode with the formation and propagation of an ionization wave. The region of low electric field intensity exists between the needle electrode and the head of the ionization wave, and its area increases continuously. The obvious voltage drop and local electric field enhancement occur between the head of the ionization wave and the plane electrode. Electron attachment reactions e + O2 → O + O− and e + 2O2 → O2− + O2 produce negative ions O− and O2−. More than 80% of the positive ions O2+ and H2O+ come from Penning ionizations between He* and molecules O2 and H2O. e + O2 → e + O + O(1D) is the main pathway to generate O and O(1D). O(1D) + H2O → 2OH and O + H + H2O → OH + H2O produce 69.3% and 39.2% of OH, respectively. 2O2 + O → O3 + O2 is the key generating reaction of O3.

(Invited) Electrochemistry in Plasmas: From Flames to RF Plasma Jets

As electrochemists, we are interested in electron attachment and detachment processes. Traditionally, we control the availability of electrons via an electrically conducting solid and measure electron transfer across the solid/liquid interface. Of course, there are exceptions to this picture, e.g. liquid/liquid interfaces, but often liquids are involved to provide an electrolyte medium to support the chemical species. Gaseous electrolytes have typically been ignored due to their feeble electrical conductivity. However, recently with the advent of new accessible approaches to form stable plasmas, these electrically conducting gases are attracting some significant interest and are now being investigated as exotic electrochemical environments.The defining property of plasmas is presence of free electrons; because of this they may be considered as both electrodes or electrolytes1, 2. We describe results supporting both modes.As electrodes, we show that metal oxides on surfaces may be reduced to zero valent metals using a helium atmospheric plasma jet.3 We show that free electrons do indeed reduce a copper oxide film, which may be carefully controlled by surface bias.4 A gaseous flame doped with electroactive species may be considered as electrolytes. Using a three-electrode system5, we may measure unique voltammograms for a series of small organic molecules and amino acids.6 Except for leucine and isoleucine, all were distinguishable. The reduction signatures originate from specific electron attachment reactions of radicals formed via incomplete combustion and fragmentation of the parent molecules. In this case without a solvent we have an extended potential window and our voltammograms extend between 0 and -10 V, which gives unprecedented access to chemistry not previously accessible in liquids. Moreover, mass transport properties are far better than in liquids, as such the fluxes of electroactive species to the electrode a much greater.

Electron number density measurements in nanosecond repetitively pulsed discharges in water vapor at atmospheric pressure

This article reports on experiments in a nonequilibrium plasma produced by nanosecond repetitively pulsed (NRP) spark discharges in water vapor at 450 K and atmospheric pressure. The objective is to determine the electron number density in the post-discharge, with spatial and temporal resolution, to gain a better understanding of the discharge development and chemical kinetics. Electron number densities were measured in water vapor from the broadenings and shifts of the Hα and Hβ lines of the hydrogen Balmer series and of the atomic oxygen triplet at 777 nm. For an average reduced electric field of about 150 Td, high electron densities up to 3 × 1018 cm−3 are measured at the cathode, up to 5 × 1017 cm−3 at the anode, and up to 4 × 1016 cm−3 in the interelectrode gap. The high density near the electrodes is attributed to ionization enhancement and secondary electron emission due to the high electric field in the plasma sheath. In the middle of the inter-electrode gap, we show that the electron density mainly decays by electron attachment reactions. The dissociation fraction of water vapor is estimated to be around 2% in the middle of the gap.

Rate versus Free Energy Change for Attaching Highly Mobile Electrons to Molecules in Nonpolar Liquids.

The inverted region of the Marcus theory, usually absent for bimolecular electron transfer reactions, is clearly observed for electron attachment reactions to molecules in nonpolar fluids. Application of pressure increased the energies of the solvated electron reactants letting us continuously adjust the free energy change. Inverted behavior is enabled by the very high mobilities of the solvated electrons which raise the diffusion-controlled encounter rates so high that they do not limit the reaction rates. The nonpolar media used in these experiments reduce reorganization energies, enhancing inverted behavior. Still, for every case showing an inverted region, the presence of low-lying excited states in the product radical anions led to regions of increasing rate constants that began at the energies of excited states of -0.54 to -1.2 eV. While continuum models predict no solvent reorganization energy in nonpolar liquids, fits to the data found solvent reorganization energies of 0.05-0.4 eV supporting ideas advanced in theories of Matyushov.

Sensitive Detection of Gas-Phase Glyoxal by Electron Attachment Reaction Ionization Mass Spectrometry.

Glyoxal (GLY) acts as a key contributor to tropospheric ozone production and secondary organic aerosol (SOA) formation on local to regional scales. The detection of GLY provides useful indicators of fast photochemistry occurring in the lower troposphere. The fast and sensitive detection of GLY is thus important, while traditional chemical ionization such as the proton-transfer reaction (PTR) is extremely limited by the poor detection limit and extensive fragmentation. To address these limitations, electron attachment reaction (EAR) ionization was applied to detect GLY. The generation of parent anions (GLY-) without fragmentation was observed, and cryogenic photoelectron imaging spectroscopy further characterized the structure of GLY-. The detection limit was estimated to be as low as (52 ± 1) pptv (parts per trillion by volume) with 1 min measurements. Other components in ambient air, such as water, carbon dioxide, and trace gases (acetone, propanal, etc.) have no effect on the detection of GLY. The EAR ionization is more promising than PTR ionization in detecting GLY. The detection of GLY in ambient air by the EAR ionization has been demonstrated.

Cycloaddition of molecular dinitrogens: formation of tetrazete anion (N4-; D2h) through associative electron attachment

State-specific reaction dynamics induced through the resonant attachment of a low energy electron (LEE) offers hitherto unavailable opportunities for the chemical synthesis of theoretically possible chemical structures. Using ab initio quantum chemical methods, this possibility is illustrated for the cycloaddition reaction of dinitrogen molecules to produce the anion of tetrazete , which is an all-nitrogen cyclic molecule. This LEE induced cycloaddition reaction, which is an associative electron attachment reaction, is initiated by the resonant attachment of a near 12 eV LEE to the dimer of non-interacting molecular dinitrogens, (N). The resulting 2p1h state of the (N) undergoes a barrierless cycloaddition reaction and produce N. In this reaction, the kinetic energy of the LEE is stored in the geometrical metastable structure of and make this process a potential method for storing energy.