Dissociative ionization of O2 and N2 by electron impact — N+ and O+ kinetic energies and angular distributions

An apparatus containing cross molecular and pulsed electron beams has been used to obtain distributions in kinetic energy and angle of fast (? 0.5 eV) positive ions produced through dissociative ionization of N₂ and O₂ by impact of 50 to 2000 eV electrons. Four main O⁺ ion groups are observed with peak energies of 0.8, 2.0, 3.0, and 5.0 eV. Two main N⁺ groups peaking at 2.0 and 3.0 eV are seen. Angular distributions of both N⁺ and O⁺ ions are essentially isotropic for electron-beam-ion detection angles from 30° to 110°.     

Reactions leading to the formation of O-3 on magnesium oxide

Ozonide ions were observed on MgO upon irradiation (254 nm) in the presence of O₂ at 25°C or upon reaction of O^-₂ on the surface with N₂O at 100°C. In the former case on O^-₂ intermediate is photodissociated to O and O^-. The latter subsequently reacts with O₂ forming O^-₃.     

Radiolysis of tetrachloromethane-water two-phase systems

The radiolysis of two-phase systems CCl₄-water proceeds in kinetical regime up to dose 12 kGy. Groos radiation yields of chloride ions are the same as the radiolysis of saturated solutions in this period. A two-phase rule of additivity is valid and the partial yields for both phases were calculated; G_CCl4(Cl^- = 5.61 ± 0.10 and G_H2O(Cl^-) = 8.29 ± 0.51 molecules/100 eV, respectively.The radiolysis proceeds in diffusional regime at the absorbed dose of more than 50 kGy. The gross radiation yield of chloride ions is determined by hydrolysis of molecular chlorine which is produced with G(Cl₂) = 0.68 ± 0.14 molecules/100 eV. An additional part of chloride ions is produced by radiolysis of substrates which diffuse into both phases with value G_dif(Cl^-) = 2.38 ± 0.31 molecules/eV. This value is approximately three times less than the gross radiation yields in kinetical regime of radiolysis of two-phase systems in saturated solutions of these substrates.     

Identifying the O2 diffusion and reduction mechanisms on CeO2 electrolyte in solid oxide fuel cells: A DFT + U study

The interactions and reduction mechanisms of O₂ molecule on the fully oxidized and reduced CeO₂ surface were studied using periodic density functional theory calculations implementing on‐site Coulomb interactions (DFT + U) consideration. The adsorbed O₂ species on the oxidized CeO₂ surface were characterized by physisorption. Their adsorption energies and vibrational frequencies are within ?0.05 to 0.02 eV and 1530–1552 cm^?1, respectively. For the reduced CeO₂ surface, the adsorption of O₂ on Ce⁴⁺, one‐electron defects (Ce³⁺ on the CeO₂ surface) and two‐electron defects (neutral oxygen vacancy) can alter geometrical parameters and results in the formation of surface physisorbed O₂, O₂^a? (0 < a < 1), superoxide (O₂^?), and peroxide (O₂^2?) species. Their corresponding adsorption energies are ?0.01 to ?0.09, ?0.20 to ?0.37, ?1.34 and ?1.86 eV, respectively. The predicted vibrational frequencies of the peroxide, superoxide, O₂^a? (0 < a < 1) and physisorbed species are 897, 1234, 1323–1389, and 1462–1545 cm^?1, respectively, which are in good agreement with experimental data. Potential energy profiles for the O₂ reduction on the oxidized and reduced CeO₂ (111) surface were constructed using the nudged elastic band method. Our calculations show that the reduced surface is energetically more favorable than the unreduced surface for oxygen reduction. In addition, we have studied the oxygen ion diffusion process on the surface and in bulk ceria. The small barrier for the oxygen ion diffusion through the subsurface and bulk implies that ceria‐based oxides are high ionic conductivity at relatively low temperatures which can be suitable for IT‐SOFC electrolyte materials. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009     

Dissociative electron attachment to polyatomic molecules: Ion kinetic energy measurements

Dissociative electron attachment to SO₂, NO₂, NF₃ and H₂O₂ is studied in terms of the kinetic energies of the dominant fragment ions. The O^? data from SO₂ show that the two major resonances at 4.6 and 7.2 eV respectively have the same dissociation limit. Similarly, the resonances at 1.8 and 3.5 eV in the O^? channel in NO₂ appear to have same dissociation limit of NO (X ²Π) + O^?, while the resonance at 8.5 eV appears to dissociate to give NO (a ⁴Π_i) along with O^?. We find considerable internal excitation of the neutral fragments in all these cases along with that of NF₃, whereas the negative ion resonance in H₂O₂ appears to fragment almost like a diatomic system with very little internal excitation of the OH and OH^? fragments.     

Activation and properties of Mo=O bonds in Mo/SiO2 catalysts

The existence of the charge transfer excited triplet state [Mo⁵⁺-O^-] produced by UV-irradiation of Mo/SiO₂ catalysts, and its reactivity are evidenced by experiments of photoluminescence, photoinduced metathesis, and photoreduction of CO. Mo⁵⁺ ions can be produced separately by thermal activation and O^- ions by further adsorption of N₂O on those Mo⁵⁺ ions. The latter of which are adsorbed on Mo⁶⁺ ions are found to be more reactive than O^2- of [Mo⁶⁺ =O^2-] bond. They are able either to add a molecule such as CO or C₂H₄, or to abstract hydrogen from H₂, CH₄ or trans-dicyanoethylene, or a CN group form tetracyanoethylene (TCNE). The Mo⁵⁺ ions are able to coordinate gas phase ligands when their coordination sphere possesses vacant sites. This is the case for tetracoordinated Mo⁵⁺ _4c ions arising from reduction of tetrahedral Mo⁶⁺ ions (Eq. (7)). These Mo⁵⁺ _4c ions are similar to those produced by UV-irradiaiion (Eq. (2)). In addition, if the adsorbed molecule has a sufficiently large electron affinity, such as TCNE or O₂, an electron transfer can occur (Eq. (9) and (17)). The [Mo⁵⁺-O^-] bond obtained by thermal activation is more difficult to evidence than that obtained with UV-activation because it is not detectable by EPR. However, the EPR results obtained at low temperature show that the O^- ions adsorbed on Mo/SiO₂ catalysts as well as the [Mo⁵⁺-O^-] excited triplet state obtained by UV-irradiation of 1Mo⁶⁺=O²] interact with methanol (Eq. (16)). They are consistent with the mechanism of methanol oxidation occurring at high temperature (Eq. (4)).     

AOT微乳液中通过水化电子产额调控合成BaSO_4纳米纤维

通过γ-辐照含有K2S2O8和BaCl2的二(2-乙基己基)琥珀酸酯磺酸钠(AOT)反相微乳液,将S2O82-通过辐射还原实现了SO42-的原位缓释,从而成功制备出BaSO4纳米纤维单晶,并进一步制得多层次的纳米纤维束结构.在此基础上,通过改变水与表面活性剂物质的量之比(ω值)、改变钡盐阴离子和在微乳液连续相添加芳香化合物等手段来调节水化电子(e-aq)产额,控制微乳液水池中S2O82-的还原和SO42-的缓释速率,成功实现了对BaSO4纳米粒子形貌的调控:随着ω值的增加或剂量率的增加,e-aq产额增加,从而加快了SO42-的释放,不利于BaSO4纳米纤维的生成;采用Ba(NO3)2为钡源时,NO3-能有效地降低e-aq产额和S2O82-的还原速率,因而在较高的剂量率和较高ω值下能得到BaSO4纳米纤维;在微乳液油相中加入甲苯来捕获油相中过量电子(e-oil),降低e-aq产额,从而在较高的剂量率下得到BaSO4纳米纤维.研究结果表明:通过e-aq产额调控纳米粒子形貌的机理在BaSO4纳米粒子的制备中得到很好体现.     

Kinetic energy release distribution in the fragmentation of energy-selected iodopropane ions

The technique of threshold photoelectron-photoion coincidence (PEPICO) has been employed to determine the average kinetic energy release and the kinetic energy release distribution (KERD) for the iodine loss from 1- and 2-iodopropane ions as a function of the ion internal energy. The KERDs at all precursor-ion energies investigated (0–3 eV excess energy) have the shape of statistically expected distributions, 1-iodopropane ions which dissociate with an apparent 0.16 eV reverse activation barrier, are shown to isomerize at low energies prior to dissociation, to produce subsequently the 2-propyl C₃H₇^? structure. At high energies they may form a different C₃H₇^? isomer. The experimentally observed average kinetic energy releases are approximately a factor of 2 greater than expected statistically suggesting that not all vibrational modes participate in the energy disposal. The secondary dissociation of the C₃H₇^? isomers to C₃H₃ which is inhibited by a reverse activation barrier of = 0.4 eV indicates that the 1- and 2-iodopropane ions dissociate 75% and 60% respectively, to form the excited 1(²P_1/2) atoms.     

Mass spectra of ethenol and its deutero analogues

Ethenol, 1-d-ethenol, O-d-ethenol and Z-2-d-ethenol were prepared by pyrolysis of corresponding 5-norbornenols at 800^°C/2 × 10^?6 Torr. The most important fragments in the electron impact mass spectrum of ethenol are [C₂H₃O]⁺ and CHO⁺ and CH₃˙. The hydrogen atom eliminated from the molecular ion comes mainly from the hydroxyl group (68%) and to a lesser extent from C(1) (25%) and C(2) (7%). The loss of the hydroxyl hydrogen is preceded by rate-determining migration of the hydrogen atom from C(1) onto C(2) to yield CH₃C?OH⁺˙ions that decompose to CH₃CO⁺ and H˙. The loss of deuterium from O-d-ethenol shows a very small primary isotope effect (k_H/k_D=1.07), whereas a significant effect is observed for the loss of hydrogen from 1-d-ethenol (k_H/k_D=1.28). The appearance energy of [C₂H₂DO]⁺ from 1-d-ethenol, AE=11.32 eV, gives a critical energy for the hydrogen loss, E=203 kJ mol^?1, which is 90 kJ mol^?1 above the thermochemical threshold for CH₃CO⁺+H˙. The appearance energy of CDO⁺ from 1-d-ethenol was measured as 12.96±0.07 eV, which sets the barrier to isomerization to CH₃CDO⁺˙ at 1121 kJ mol^?1. The ionization energy of ethenol was found to be 9.22±0.03 eV.     

Radiation effects in plutonium and carbonate co-doped calcium hydroxy apatite: An EPR study

Electron paramagnetic resonance studies were conducted on synthetic calcium hydroxy apatite samples co-doped with ²³⁹Pu and carbonate ion. These investigations were carried out to assess the self-irradiation effects in bone and teeth on exposure to plutonium, as calcium hydroxy apatite is the major constituent of bone and teeth. On self-irradiation, in addition to the signal from O^- ion arising from the radiolysis of hydroxide ion, EPR signals due to CO₂ ^-, PO₂ ^2- and another signal assigned to surface O^- ions were observed in the samples. In freshly quenched gamma irradiated samples, signals from CO₃ ^-, O^- , PO₂ ^2- and O₂ ^- ions were observed. The EPR signal of O₂ ^- ion shows a doublet splitting suggesting that O₂ ^- ion gets preferentially stabilized close to Pu⁴⁺. The radiation damage due to Pu⁴⁺ at Ca²⁺ sites, in the sample appears to be lower as compared to that due to external gamma-irradiation. Moreover, the alpha-dose in ²³⁹Pu doped samples has self-annealing effects. These are attributed to localized radiation damage due to alpha-particles compared to evenly distributed radical ions produced due to gamma-irradiation.     

Thermal-energy charge transfer of Ar+ with H2O: Internal and kinetic energy of the product H2O+

The reaction of Ar⁺ with H₂O has been investigated at near-thermal energy. The product ions H₂O⁺ and ArH⁺ account for 90 and 10% of the total reaction rate, respectively. Kinetic energy measurements and emission spectroscopy of the H₂O⁺ product ions are reported. It is concluded that at least 60% of H₂O⁺ ions are in the X? state with ≈2.4 eV vibrational energy while up to 40% are in the à state with a mean vibrational energy of 1.4 eV; the à state vibrational distribution has been determined. It is shown that both H₂O⁺ states are populated via an energetically “non-resonant” charge transfer process.     

Production and properties of CO2 cluster anions

Stoichiometric and non-stoichiometric negatively charged CO₂ cluster ions have been produced in a crossed neutral cluster/electron beam ion source. The abundance and stability of these ions have been studied with a double focussing sector field mass spectrometer. The observed abundance anomalies (“magic numbers”) in the mass spectra of (CO₂) _n ^? and (CO₂) _n O^? ions correlate with corresponding small and large metastable fractions of these ions (for loss of one CO₂ unit). Variation of the measured metastable fractions as a function ofn are related to corresponding changes in the monomer binding energies. In addition, we have observed for the first time (CO₂) _n O ₂ ^? ions (i.e. at electron energies above 8 eV with an energy resonance at about 14 eV) and we discuss possible production mechanisms for these ions. Relative electron attachment cross sections have been determined in the energy regime O<E≦20 eV for (CO₂) _n ^? , (CO₂) _n O^? and (CO₂) _n O ₂ ^? withn=1 to 20. The shape of the cross section function for (CO₂) _n O^? is strongly dependent on the cluster sizen.     

Vibrational structure in kinetic energy spectra of O+ ions from electron impact dissociative ionization of O2: Predissociation of the B 2Σg− state of O2+

Structure has been observed in the ≈ 0.8 eV kinetic energy O⁺ ion peak produced by electron impact dissociative ionization of O₂. The spacing between the features observed is approximately 0.08 eV which is consistent with their originating through predissociation of the B ²Σ_g^? state of O⁺.     

Exploration of Metal-Metal Charge Transfer (MMCT) and its Effect in Generating New Colored Compounds in Mixed Metal Oxides

Compounds belonging to the palmierite structure, (Zn_3−xM_x)A₂O₈ (M=Co, Ni, Cu and A=V, P) have been prepared employing solid state methods. The transition metal substituted compounds of Zn₃V₂O₈ exhibits colors that are unique varying from mint green to forest green for Co²⁺ ions. The observed colors were understood based on the allowed d-d transitions and metal to metal charge transfer (MMCT) transitions. The MMCT transitions involve partially filled d-orbitals of Co²⁺ (3d⁷), Ni²⁺ (3d⁸), and Cu²⁺ (3d⁹) ions and the V⁵⁺ ions (3d⁰). The spinel compounds, Zn_2−xCo_xMO₄ (M=Ti, Sn) were also prepared to understand the MMCT transitions in the compounds. Band structure calculations were carried out to understand the participating orbitals near the Fermi level and the band gap. The calculations support the idea that the substitution of transition elements in the palmierite structure reduces the overall band gap from 3.18 eV for Zn₃V₂O₈ to 2.61 eV Zn_2.5Co_0.5V₂O₈ compound. This indicates the substitution of transition elements provide a tool towards band gap engineering.     

Electron attachment to oxygen and oxygen/ozone clusters studied in a high-resolution crossed beams experiment

Highly monochromatized electrons (with 30 meV FWHM) are used in a crossed beams experiment to investigate electron attachment to oxygen clusters (O₂)_n at electron energies from approximately zero eV up to 2 eV. At energies close to zero the attachment cross section for the reaction (O₂)_n +e → O ₂ ^? varies inversely with the electron energy, indicative of s-wave electron capture to (O₂)_n. Peaks in the attachment cross section present at higher energies can be ascribed to vibrational levels of the oxygen anion. The vibrational spacings observed can be quantitatively accounted for. In addition electron attachment to mixed oxygen/ozone clusters has been studied in the energy range up to 4 eV. Despite the initially large excess of oxygen molecules in the neutral clusters the dominant attachment products are undissociated cluster ions (O₃) _m ^? including the O ₃ ^? monomer while oxygen cluster ions (O₂) _n ^? appear with comparatively low intensity.     

Kinetic study of the reaction between [Re2O3(CN)8]4- and cyanide ions

A kinetic study of the reaction between [Re₂O₃(CN)₈]^4- and cyanide ions indicated that [ReO₂(CN)₄]^3- and [Re(CN)₇]^4-, the final products, are both generated at a rate of 1.30(8)×10^-4s^-1 at 38.2°C and pH=12. From the nonlinear kinetics, it is deduced that cyanide ions react with [Re₂O₃(CN)₈]^4- in a fast equilibrium step followed by slow decomposition to give [ReO₂(CN)₄]^3- as the first product and [Re(CN)₇]^4- after a subsequent fast reduction and substitution step. The activation parameters H 54(7)kJ mol^-1 and S = -145(22)J K^-1 mol^-1 were determined.     

Effect of Ammonium Ions on the Electroreduction of Anions at a Mercury Electrode

The effect of ammonium ions on the electroreduction of peroxodisulfate (S₂O^2- ₈) and perbromate (BrO^- ₄) anions is found to be commensurate with that of potassium ions. Ammonium ions accelerate the reduction of iodate (IO^- ₃), bromate (BrO^- ₃), and chromate (CrO^2- ₄) anions in nonbuffered solutions and does not, in buffered ones. In the former case, the effect is connected with the pH change in the near-electrode layer during the reaction and with the participation of ammonium ions in hydrolytic equilibriums, rather than with a simultaneous transfer of ammonium ions and electrons in an elementary act. The conclusions in the literature in favor of a simultaneous transfer of the proton and electron in the proton-consuming reactions of reduction of anions is shown to be ambiguous.     

The observation of predissociations in the oxygen molecular ion by low-energy electron impact

The kinetic energy distribution of the O⁺ ions formed by dissociative ionization of O₂ has been carefully examined in the range of 0.0 to 1.3 eV. In the peak at 600 meV fine structure is observed and interpreted by predissociation. The high energy side of the peak has been ascribed to the predissociation of the ²Δ_g, B²Σ^?_g and the C⁴Σ^?_u states of O⁺₂. The low energy side of the peak is presumably due to the predissociation of the b⁴Σ^?_g state or the ²Φ_u state of O⁺₂ or to autoionizing predissociation.     

Vertical triple ionization of ethyne molecules in triple-electron-transfer collisions with O beam ions

Triple-electron-transfer (TET) collisions of 6 keV O²⁺ beam ions with gas-phase ethyne molecules were studied with mass spectrometric techniques. Measurement of the kinetic energies of the O⁻ ions produced yielded triple-ionization energies (TIEs) of ethyne to states of its triply charged positive ion, once those transitions corresponding to the transfer of three electrons in a single collision were identified: eight such peaks were found between 65.1 and 80.1 eV. Possible O²⁺ states in the beam include ³P, ¹D, ¹S; according to spin conservation the singlet ions should populate only doublet states of C₂H₂³⁺, while projectiles in triplet states would populate both its doublet and quadruplet states. Using ab initio propagator calculations for the triple-ionization transitions, the TIEs and quantum numbers for the states of C₂H₂³⁺ associated with each peak observed in the TET spectrum could be identified. The overall match between the theoretical and experimental energies was good, so that it could be established that the population of quadruplet states was comparable in intensity with that for doublets. This is consistent with previous evidence for O²⁺(³P) being the dominant state in the projectile beam used.     

Survey of reaction types in low-energy colliosional activation of protonated methyl alkyl ketones

In contrast to high-energy collisions, where simple cleavages are commoner, rearrangements typically account for 96–100% of products in low-energy collisions of the [M + 1]⁺ ions of aliphatic methyl ketones. Rules for predicting low-energy helium collsional-activated decomposition (CAD) spectra of the ketones are based on proton affinities of fragments formed by simple rearrangements. The commonest reaction is equivalent to the energetically improbable four-center 1,3-H or 1,3-R shift; other rearrangements equivalent to processes with five-, six-, or seven-center activated complexes are less important. In larger ions, loss of water followed by loss of alkene dominates. O-Protonated enol forms either lose water to give a carbonium ion that rearranges to forms capable of losing olefin fragments, or rearranges to an intermediate in the formation of acetyl ion and an alkane. O-Protonated keto forms rearrange to alkanes and protonated smaller carbonyl compounds. The ion kinetic energies necessary to produce several intense daughter ions at threshold establish the order of sequential fragmentations. When helium is the collisional gas and the ion energy is 30 eV in the laboratory frame (the maximum value studies), the ion energy is only 0.8–1.9 eV in the center-of-mass frame depending on its size. Only a fraction of this kinetic energy is converted to internal energy, so that onsets of reaction channels differing by several tenths of an electron-volt are easily studied. Some isomers of methyl ketones can be easily distinguished by He-CAD spectra of their [M + 1]⁺ ions.