Neutral Oxygen Atoms Research Articles

Neutral Dissociation of Superexcited Oxygen Molecules in Intense Laser Fields

Superexcited states (SESs) of oxygen molecules and their neutral dissociation processes have been studied both experimentally and theoretically using intense femtosecond laser. We find that at the laser intensity of approximately 2 x 10(14) W/cm(2), ultrashort laser pulse causes neutral dissociation of oxygen molecule by way of SESs. The dissociation products are the excited neutral oxygen atoms, which are observed through fluorescence spectroscopy. Laser power dependence of the fluorescence intensity shows that each molecule effectively absorbs an average of ten laser photons. The total energy absorbed is sufficient to stimulate the molecule to many of the SESs. The effect is equivalent to single photon excitation in the extreme-ultraviolet (XUV) region by synchrotron radiation (SR). Morse potential energy curves (PECs) are constructed for the SESs of O(2) molecules. In light of the PECs, predissociation mechanism is proposed for the neutral dissociation. Quasi-classical trajectory (QCT) calculations show that the predissociation time is as short as 100 fs, which is consistent with our experimental measurement using ultrafast pump-probe technique.

Upper thermospheric ion-neutral coupling from combined optical and radar experiments over Svalbard

Abstract. The response of thermospheric neutral parameters such as winds and temperatures to rapid changes in geophysical conditions has usually been considered to be relatively slow, on the order of hours, and steady, representing an integration of more rapid ionospheric changes. Quantifying the relevant ion-neutral coupling has proved difficult due to a lack of relevant laboratory data for the most important collisions, namely between neutral atomic oxygen and its first ion. As a result the representation of ion-neutral coupling in numerical models of the upper atmosphere has often produced poor comparison to experimental data. Using a unique combination of spatially extended ion and neutral thermospheric parameters we show that the neutral response can be very rapid, within 15 min, to imposed forcing via ion-neutral coupling. The array of complementary instrumentation measuring the thermosphere above Svalbard in the Northern Hemisphere allows detailed study of the causes and effects from both the ion and neutral perspectives. The implications for development and testing of the thermospheric numerical models is discussed.

Degradation of Staphylococcus aureus bacteria by neutral oxygen atoms

The degradation of Staphylococcus aureus bacteria during treatment with neutral oxygen atoms was monitored by scanning electron microscopy. Experiments were performed in an afterglow chamber made from borosilicate glass. The source of oxygen atoms was remote inductively coupled radiofrequency oxygen plasma. The density of atoms at the samples was 8×1020 m−3. The treatment was performed at room temperature. The first effect was the removal of dried capsule. Capsule on exposed parts of bacteria was removed after receiving the dose of 6×1023 at./m2, while the parts of capsule filling the gaps between bacteria were removed after receiving the dose of 2.4×1024 m−2. After removing the capsule, degradation continued as etching of bacterial cell wall. The etching was rather nonuniform as holes with diameter of several 10 nm were observed. The cell wall was removed after receiving the dose of about 7×1024 m−2. The etching probabilities were about 2×10−5 for the capsule and 2×10−6 for the cell wall. The results were explained by different compositions of capsule and the cell wall.

A threshold photoelectron-photoion coincidence spectrometer with double velocity imaging using synchrotron radiation

A novel threshold photoelectron-photoion coincidence (TPEPICO) imaging spectrometer at the U14-A beamline of the Hefei National Synchrotron Radiation Laboratory is presented. A set of open electron and ion lenses are utilized to map velocity imaging of photoelectrons and photoions simultaneously, in which a repelling electric field using an extra lens is applied to magnify images of photoelectrons instead of traditional accelerating electric field in order to suppress the contribution of energetic electrons in the threshold photoelectron spectroscopy (TPES) and the mass-selected TPEPICO spectroscopy. The typical energy resolution of TPES is measured to be 9 meV (full width at half maximum), as shown on the (2)P(1/2) ionization of argon. The measured mass resolving power for the present TPEPICO imaging spectrometer is above 900 of M/DeltaM. Subsequently as a benchmark, oxygen molecule is photoionized by monochromatic synchrotron radiation at 20.298 eV and dissociates to an oxygen atomic ion and a neutral oxygen atom, and the translation energy distribution of oxygen atomic ion is measured by the time-sliced imaging based on mass-selected TPEPICO experiment. The kinetic energy resolution of the present ion velocity imaging is better than 3% of DeltaE/E.

Electronic feshbach resonances created in soft x-ray-induced 02 dissociation

When an atom or molecule is ionized by an x-ray, super-excited states can be created that then decay, or autoionize, by ejecting a second electron from the ion. Here we find that autoionization following soft x-ray photoionization of molecular oxygen follows a complex, multi-step, process[1]. By interrupting the autoionization process using a short laser pulse, we show that autoionization cannot occur until the internuclear separation of the fragments is greater than 30 Ångstroms. As the ion and excited neutral atom separate, we directly observe the birth of a new state. We follow the transformation of electronically bound states of the molecular ion into Feshbach resonances of the neutral oxygen atom that are characterized by both positive and negative binding energies. States with negative binding energies have not been predicted or observed in neutral atoms previously.

UV-visible emission as a probe of core excitations applied to the furan and carbon dioxide molecules

The core excitations of the furan and carbon dioxide molecules have been studied using dispersed UV-visible fluorescence spectroscopy. Balmer-α (Balmer-β) emission was measured at the O 1s and C 1s (O 1s) excitations of furan, while emission due to an excited state of the neutral oxygen atom was measured at the O 1s excitations of CO2. The excitation functions of the emission lines display both valence and Rydberg resonances, but the latter are more enhanced.

Autoionization dynamics and Feshbach resonances: Femtosecond EUV study of O2 excitation and dissociation

In this work, we present a time-domain study of the complex, multi-step, evolution of highly excited states of oxygen (O2) that result from EUV photoionization. By monitoring the dissociation of molecular oxygen ions, we show that autoionization cannot occur until the internuclear separation is 30 Å or greater. As the ion and excited neutral atom separate, we directly observe the transformation of electronically bound states of the molecular ion into Feshbach resonances of the neutral oxygen atom. We achieve this by using laser high-harmonics in a femtosecond EUV-IR pump-probe scheme, combined with a triple coincidence reaction microscope measurement. Finally, we show control of the dissociation pathway through IR pulse induced ionization.

First-Principles Calculations on the Geometry and Electronic Structure of Rutile TiO<sub>2</sub> (110) Surface

In this paper, both geometrical and electronic properties of rutile TiO2 (110) surfaces have been investigated using First-Principles Density-Functional calculations with CASTEP code, the model of stoichiometric surface is a (2x1) super-cell which has 12 atomic-layer slabs with the bottom 6 held fixed, the bridging-oxygen vacancy surface has been constructed by removing a neutral bridging oxygen atom from this surface. For the stoichiometric surface, the atom relaxations are: Ti6f (+0.2865Å), Ti5f (-0.1039Å), O3f (+0.2433Å) and Ob (+0.0075Å), we find no reconstruction and no surface states in the band gap, the density of states (DOS) is similar to the bulk except the lower conduction band intensity, in accord with recent experiments. Whereas, as a result of bridging-oxygen vacancy, the atom relaxations exchanged and reconstruction occur. The 2 excess electrons left behind removal of one bridge O atom are localized on the Ti-t2g conduction band orbitals, convert some of the Ti4+ ions into Ti3+ ions and result a compensatory shift in the Fermi level. The band gaps we calculated for stoichiometric surface is similar to the bulk, but its increase can be found for Ob vacancy surface.

Double Photoionization of CO2 Molecules in the 34−50 eV Energy Range

The double photoionization of CO(2) molecules has been studied in the 34-50 eV photon energy range, by the use of synchrotron radiation and detecting electron-ion and electron-ion-ion coincidences. Three processes have been observed: (i) the formation of the CO(2)(2+) molecular dication, (ii) the production of a metastable (CO(2)(2+))* that dissociates, with an apparent lifetime of 3.1 micros, giving rise to CO(+) and O(+) ions, and (iii) the dissociation leading to the same products, but occurring with a lifetime shorter than 0.05 micros. The relative dependence on the photon energy of the cross section for such processes has been measured. While for the production of the molecular dication a threshold is observed, in agreement with the vertical threshold for double ionization of CO(2), for the dissociative processes the threshold appears to be lower than that value, indicating the presence of an indirect dissociation, probably leading to the formation of CO(+) together with a neutral autoionizing oxygen atom.

Determination of the neutral oxygen atom density in a plasma reactor loaded with metal samples

The density of neutral oxygen atoms was determined during processing of metal samples in a plasma reactor. The reactor was a Pyrex tube with an inner diameter of 11 cm and a length of 30 cm. Plasma was created by an inductively coupled radiofrequency generator operating at a frequency of 27.12 MHz and output power up to 500 W. The O density was measured at the edge of the glass tube with a copper fiber optics catalytic probe. The O atom density in the empty tube depended on pressure and was between 4 and 7 × 1021 m−3. The maximum O density was at a pressure of about 150 Pa, while the dissociation fraction of O2 molecules was maximal at the lowest pressure and decreased with increasing pressure. At about 300 Pa it dropped below 10%. The measurements were repeated in the chamber loaded with different metallic samples. In these cases, the density of oxygen atoms was lower than that in the empty chamber. The results were explained by a drain of O atoms caused by heterogeneous recombination on the samples.

FAR-INFRARED DETECTION OF NEUTRAL ATOMIC OXYGEN TOWARD THE HORSEHEAD NEBULA

We present the first detection of neutral atomic oxygen (3P_1-3P_2 fine structure line at ~63um) toward the Horsehead photodissociation region (PDR). The cloud has been mapped with the Spitzer Space Telescope at far-IR (FIR) wavelengths using MIPS in the spectral energy distribution (SED) mode. The [OI]63um line peaks at the illuminated edge of the cloud at AV~0.1-0.5 (inward the gas becomes too cold and outward the gas density drops). The luminosity carried by the [OI]63um line represents a significant fraction of the total FIR dust luminosity (I_63/I_FIR~4x10^-3). We analyze the dust continuum emission and the nonlocal OI excitation and radiative transfer in detail. The observations are reproduced with a gas density of n_H~10^4 cm^-3 and gas and dust temperatures of T_k~100 K and T_d~30 K. We conclude that the determination of the OI 3P_J level populations and emergent line intensities at such ``low'' densities is a complex non-LTE problem. FIR radiative pumping, [OI]63um subthermal emission, [OI]145um suprathermal and even maser emission can occur and decrease the resulting [OI]63/145 intensity ratio. The Herschel Space Observatory, observing from ~55 to 672um, will allow us to exploit the diagnostic power of FIR fine structure lines with unprecedented resolution and sensitivity.

Surface functionalization of organic materials by weakly ionized highly dissociated oxygen plasma

A review on surface modification of different polymers by treatment in oxygen plasma is presented. Plasma is created in a high frequency inductively coupled gaseous discharge at the power of about 200 W. In such discharge created in pure oxygen, plasma with the following parameters is obtained: the electron temperature of about 50.000 K, the charged particle density around 1x1016 m-3, and the neutral oxygen atom density of the order of 1021 m-3. A huge flux of neutral oxygen atoms on the surface of samples exposed to plasma assures for rapid interaction with polymer materials. The modification of surface properties of the following polymers was studied: polyethyleneterephthalate (PET), polyethersulphone (PES), polyphenylenesulfide (PPS), Nylon 6 polyamide (PA6), polytetrafluoroethylene (PTFE), polystyrene (PS), polypropylene (PP) and cellulose (ink-jet paper and textile). The polymer samples were treated for 3 s in oxygen plasma at a pressure of 75 Pa where the O-atom density was the largest at 4x1021 m-3. The appearance of the functional groups on the surface of the samples was monitored by high resolution X-ray photoelectron spectroscopy (XPS). The results show that oxygen plasma treatment is an effective tool for surface modification. On all polymer surfaces increased concentration of oxygen is detected. The high resolution C1s peaks indicate formation of several new oxygen-containing functional groups. On all polymers groups like C-O, C=O and O=C-O are observed. The concentration of these groups depends on the type of polymer. The highest uptake of oxygen by the polymer was found for cellulose and the lowest for polypropylene. The only exception was polymer PTFE where practically no chemical changes were observed after plasma treatment.

Observing the Creation of Electronic Feshbach Resonances in Soft X-ray–Induced O 2 Dissociation

When an atom or molecule is ionized by an x-ray, highly excited states can be created that then decay, or autoionize, by ejecting a second electron from the ion. We found that autoionization after soft x-ray photoionization of molecular oxygen follows a complex multistep process. By interrupting the autoionization process with a short laser pulse, we showed that autoionization cannot occur until the internuclear separation of the fragments is greater than approximately 30 angstroms. As the ion and excited neutral atom separated, we directly observed the transformation of electronically bound states of the molecular ion into Feshbach resonances of the neutral oxygen atom that are characterized by both positive and negative binding energies. States with negative binding energies have not previously been predicted or observed in neutral atoms.

Ultrathin SiO2 layers on Si(111): preparation, interface gap states and the influence of passivation

An essential prerequisite for the successful application ofSi/SiO2 nanostructures in photovoltaics is the realization of well-defined and abruptinterfaces with low densities of interface gap states. Here, a complete in situprocess from preparation and hydrogen passivation to interface gap stateanalysis by near-UV photoelectron spectroscopy without breaking ultrahighvacuum (UHV) conditions is introduced. It is demonstrated that by RF plasmaoxidation of Si(111) substrates with thermalized neutral oxygen atoms, ultrathinSiO2 layers can be realized with compositionally and structurally abruptSi/SiO2 interfaces and a minimal amount of intermediate oxidation states bridging the transition from Si toSiO2. Plasmaoxidized samples have significantly lower interface gap states than samples oxidized by thermal oxidationat 850 °C. Interface gap state densities were further reduced by in situ hydrogen plasma passivationwith nearly thermalized H atoms. The resulting reduction of interface recombinationvelocity and the increase of effective majority and minority carrier lifetimes are revealed byconstant photocurrent measurements and quasi-steady-state photoconductance,respectively.

Syntheses, structures and properties of three neutral bisupporting heteropolyoxometalates

Three neutral polyoxometalates [PVW11O40{M(phen)2H2O}2] · 3H2O (phen = 1,10′-phenanthroline, M=Co 1, Zn 2, Ni 3) are composed of water and the neutral Keggin-type polyoxometallate covalently linking a pair of transition metal complex fragments on opposite sides. The transition metal lies in the center of a distorted octahedron. Multi hydrogen-bonding interactions between coordinated waters of neutral polyoxometalate molecules and terminal oxygen atoms of Keggin units and between bridging oxygens of Keggin units and lattice water create a two dimensional layer and between the layers there exist van der Waals forces. The framework of the neutral molecule begins to decompose at ca 500°C. Compound 1 exhibits a weak antiferromagnetic interaction in the 2–300 K range.

Hydrogen passivation of interfacial gap state defects at UHV-prepared ultrathin SiO 2 layers on Si(1 1 1), Si(1 1 0), and Si(1 0 0)

A complete in situ process from preparation and hydrogen passivation to interface gap state analysis by near-UV photoelectron spectroscopy (NUV-PES) without breaking ultrahigh vacuum (UHV) conditions is applied to ultrathin oxide layers on Si(1 1 1), (1 1 0), and (1 0 0). RF plasma oxidation with thermalized neutral oxygen atoms allows the growth of homogeneous ultrathin SiO 2 layers (<2 nm) and the preparation of compositionally and structurally abrupt Si/SiO 2 interfaces with minimal amounts of suboxides ranging from 2% on Si(1 0 0) to 4% on Si(1 1 0). The oxide growth is independent of the crystallographic orientation. Appropriate plasma treatment with nearly thermalized hydrogen atoms ( E kin<1 eV) leads to significant passivation of dangling bonds at the ultrathin-SiO 2/Si interfaces and is most efficient on Si(1 0 0). In contrast, energetic hydrogen plasma treatment of these interfaces with kinetic energies exceeding 120 eV, which is conventionally applied for polycrystalline Si thin-film solar cells, imparts large amounts of energy and deteriorates the electrical properties as is reflected in interface degradation and increased densities of defect states.

Oxygen atom density in capacitively coupled RF oxygen plasma

The density of neutral oxygen atoms was determined in a plasma reactor for surface functionalization of polymer materials. Plasma was created in a stainless steel chamber by capacitively coupled RF generator at 13.56 MHz and adjustable forward power up to 100 W. Measurements were performed with a classical nickel catalytic probe. Systematic measurements were performed at a constant pumping speed, different flow rates from 15 to 100 sccm corresponding to pressures between 30 and 110 Pa, different powers between 40 and 100 W and different probe positions in the discharge chamber. The results showed that the O atom density did not depend much on probe position as long as it was between the powered electrode and grounded housing facing the electrode. The O density depended rather linearly with power at fixed pressure. At low power, the O density did not depend much on pressure, but at high power, it was increasing with increasing pressure. The O density was of the order of 10 19 m −3 and increased slightly over 10 20 m −3 at the highest power and pressure. The results were explained by gas phase and surface reactions.

Catalytic probes with nanostructured surface for gas/discharge diagnostics: a study of a probe signal behaviour

Catalytic probes are used for plasma diagnostics in order to quantify the density of neutral atoms. The probe response primarily depends on the probe material and its surface morphology. Here we report on the design, operation and modelling of the response of niobium pentoxide sensors with a flat and nanowire (NW) surfaces. These sensors were used to detect neutral oxygen atoms in the afterglow region of an inductively coupled rf discharge in oxygen. A very different response of the flat-surface and NW probes to the varying densities of oxygen atoms was explained by modelling heat conduction and taking into account the associated temperature gradients. It was found that the nanostructure probe can measure in a broader range than the flat oxide probe due to an increase in the surface to volume ratio, and the presence of nanostructures which act as a thermal barrier against sensor overheating. These results can be used for the development of the new generation of catalytic probes for gas/discharge diagnostics in a range of industrial and environmental applications.

Al-induced reduction of the oxygen diffusion inHfO2: an ab initio study

Using first-principles calculations we have studied the effect of Aladdition on the diffusion of interstitial oxygen atoms and ions inHfO2.Calculated results show that interstitial oxygen ions in the singly negatively charged state easily diffusein HfO2 via exchange with lattice oxygen atoms, due to the lower diffusion barrier as compared to thosefor neutral interstitial oxygen atoms and interstitial oxygen ions in the doubly negativelycharged state. The addition of Al raises the diffusion barrier for interstitial oxygen becausethe interstitial oxygen is strongly attracted by its neighboring Al atoms. The electronicstructure analysis further reveals that the bonding between interstitial oxygen andlattice oxygen atoms is strengthened for each charge state of interstitial oxygen inHfO2 with the addition of Al.

Rf plasma system as an atomic oxygen exposure facility

The materials of spacecraft external surfaces in low Earth orbit (LEO) are exposed to the various constituents of the space environment, including atomic oxygen (AO) and solar ultra violet (UV) radiation. Material degradation and erosion by LEO are simulated in ground laboratories using a variety of experimental facilities, each with their respective limitations. rf oxygen plasma is a simulation facility widely used for materials screening for LEO application. However, the complex plasma environment, which contains, in addition to the neutral oxygen atoms, excited species, electrons, and ions as well as vacuum ultraviolet (VUV) radiation, might lead to erroneous determination of materials reactivity with respect to LEO. This paper describes the development of a simple, low cost rf plasma system to produce a well-defined AO and VUV environment. The new system constrained the afterglow flow through two right-angle turns. The afterglow was characterized at three specific locations by (i) optical emission spectroscopy for assessment of electronically excited states, (ii) current measurements, and (iii) UV radiation measurements. KaptonR samples were exposed at the three specific locations in the system and characterized by mass loss for etch rate evaluation, and atomic force microscopy for surface modification. It was found that there is a significant reduction in ionic species, excited species, and UV radiation as the afterglow advances through the right-angle turns. The reduction in charged particle flux is due to recombination within the afterglow as well as neutralization by colliding with the grounded metal chamber walls; similar decrease in UV radiation flux occurs through radiation absorption by the chamber walls. Finally, it is shown that the ground state AO is the dominant reactive specie of the plasma afterglow after passing through the two right-angle turns.