Negative ions of hydrogenated and deuterated C60 fullerenes

This paper reports on the results of mass spectrometric and theoretical investigations of hydrogenated and deuterated fullerene derivatives C₆₀H(D)_x. The formation and decay (through electron autodetachment) of negative molecular ions of the C₆₀H₁₈ and C₆₀D₁₈ hydrofullerenes are discussed. A comparative analysis of these processes is performed for different fullerene derivatives.     

Untersuchung der unelastischen Wechselwirkung langsamer monoenergetischer Elektronen mit einfachen Kohlenwasserstoff-Molekülen I.Elektronenanlagerungs-Wirkungsquerschnitte in Abhängikeit von der Elektronenenergie und vom Molekülaufbau

Investigation of the Inelastic Interaction of Slow Monoenergetic Electrons with Simple Hydrocarbon Molecules. I. Dependence of the Electron Attachment Cross Sections on Electron Energy and on Molecular Structure The formation of negative ions from a series of simple hydrocarbons was studied experimentally via an interaction of hydrocarbon molecules with monoenergetic electrons in the range of 0–15 eV. The ion formation is characterized by means of the attachment cross section in dependence on electron energy. Negative ions were formed as well by dissociative electron attachment as by direct electron attachment. The electron attachment is depending on electron energy, molecular seize, and on the number of unsaturated C-C-bonds in the molecule. The formation processes are discussed and the role of negative hydrocarbon ions in the plasma is estimated.     

狭缝微放电等离子体参数的光谱测量

利用平行管水电极介质阻挡放电装置,在氩气和空气混合气体中,得到了狭缝微放电等离子体。利用发射光谱法,研究了此放电中分子振动温度、分子转动温度和电子的平均能量随气体压强的变化。通过氮分子第二正带系(C3Πu→B3Πg)的发射谱线计算了氮分子的振动温度;利用氮分子离子(N2+)的第一负带系(B2Σu+→X2Σg+)的发射谱线计算了氮分子的转动温度;测量了氮分子离子391.4 nm和激发态的氮分子337.1 nm两条发射谱线的相对强度之比,研究了电子能量的变化。结果表明,当压强从60 kPa增大到100kPa,分子振动温度及分子转动温度均减小,氮分子离子谱线与激发态的氮分子谱线的强度之比亦减小。     

Slow decay of negative molecular fluorofullerene ions in the electron autodetachment process

The mean lifetimes of negative molecular ions of C₆₀ fullerene and its fluoroderivatives C₆₀F₁₈ and C₆₀F₃₆ with respect to the autodetachment of electrons have been measured as functions of the ionizing electron energy by the method of mass spectrometry of electron resonance capture. The lifetimes of negative ions in the compounds under investigation are within the one-second range, and an increase in the number of addends leads to an increase in the lifetimes of negative ions by 1.5–2.5 orders of magnitude.     

Negative Ions in a Glow Discharge of Tetrafluoromethane

The Langmuir — probe measurements in a CF₄ — glow discharge reveal a large number of negative ions (10¹⁰ cm^?3) in the plasma between the planar C-electrodes. Under special conditions the density of them exceeds the electron density at several orders of magnitude and sustains a quasi — electron free plasma. The ratio depends on the residence time of the molecular gas in the discharge reactor. It is due to dissociative electron attachment to highly molecular gas components arising from the plasmachemical conversion of CF₄. F^? and CF₃^? are the most important negative ions.     

Lifetime of negative molecular ions of tetracene and pentacene with respect to the autodetachment of an electron

The processes of nondissociative resonant attachment and autodetachment of electrons in a number of poly-cyclic aromatic hydrocarbon molecules have been investigated by mass spectrometry. Long-lived negative molecular ions of phenanthrene and triphenylene have not been observed. Such ions have been detected for anthracene, pyrene, and benzo[e]pyrene capturing thermal electrons. Negative molecular ions of tetracene and pentacene have also been observed up to 2.5–3 eV. The lifetimes of these ions with respect to the auto-detachment of an electron have been measured throughout the energy range where they are observed. This lifetime for tetracene and pentacene is more than 10 ms, which is two or three orders of magnitude larger than that for remaining compounds. Correlation between the lifetime of ions and the electron affinity of the molecules has been revealed.     

Formation of positive and negative ions of thymine molecules under the action of slow electrons

The formation of positive and negative molecules of thymine—a base of nucleic acids—under the action of slow electrons is investigated by the method of crossed electron and molecular beams. The method developed makes it possible to measure the molecular beam intensity and determine the energy dependences and absolute values of total cross sections for the formation of positive and negative ions of thymine molecules. It is found that the maximal cross section for the formation of positive ions is reached at an energy of 95 eV and its absolute value is, accordingly, 1.4 × 10^?15 cm². The total cross section for the formation of negative ions is 8.2 × 10^–18 cm² at an energy of 1.1 eV. The mass spectra of thymine molecules are measured and the cross sections of dissociative ionization are determined.     

团簇六边形斑图等离子体参数的光谱测量

在氩气和空气混合气体介质阻挡放电中,首次发现了团簇六边形斑图。运用发射光谱法,研究了此斑图中单个团簇的三种等离子体参数：分子振动温度、分子转动温度以及电子的平均能量随空气含量的变化。实验通过测量氮分子光谱并采用氮分子第二正带系(C3Π_u→B 3Π_g)计算了振动温度;同时采集氮分子离子(N+₂)的第一负带系(B 2Σ+_u→X 2Σ+_g)计算转动温度。利用氮分子离子391.4 nm和激发态的氮分子337.1 nm两条发射谱线的相对强度之比,作为研究电子平均能量的变化的依据。结果显示,当混合气体中空气含量从16%逐渐增大到24%时,三种等离子体参数均逐渐增大。     

Electron-forbidden energy gap of hydrogen in a wide pressure interval

A simple model is used for estimating the bottom energy of the electron conduction band and the electron-forbidden gap energy. It is shown that electrons in liquid hydrogen are localized not in electron bubbles, as was considered previously, but in molecular negative ions surrounded by voids about 0.5 nm in radius. The conductivity of fluid hydrogen at not very high pressures is connected to transfer of positively charged clusters and negatively charged bubbles. As the pressure and density increase, molecular dissociation occurs and electron localization on atoms becomes more favorable, also with the creation of a void around atomic negative ions. At a sufficiently high concentration of atoms, the probability of tunnel transition of an electron from one atom to another becomes close to unity, the energy level of the negative ion degenerates in the band, and the conductivity is caused by the transfer of these quasifree electrons. It is supposed that this charge transfer mechanism may play an important role in the region of fluid hydrogen metallization.     

Surface science of diamond: Familiar and amazing

The crystal structure of diamond is identical with that of its more common semiconductor relatives silicon and germanium. Consequently, a number of surface properties in terms of reconstructions, surface states and surface band diagrams are similar as in the case of Si or Ge. But diamond also exhibits a number of unusual and potentially very useful surface properties. Particularly when the surface dangling bonds are saturated by monovalent hydrogen atoms (donor-like), surface states are removed from the gap, the electron affinity changes sign and becomes negative, and the material becomes susceptible to an unusual type of transfer doping where holes are injected by acceptors located at the surface instead of inside the host lattice. These surface acceptors can in the simplest case be adsorbed molecules conveniently chosen by their electron affinity, but they can also be solvated ions within atmospheric water layers or electrolytes in contact with the hydrogenated diamond surface. In this article the surface properties of diamond will be reviewed with special emphasis on this new kind of doping mechanism.     

Observation of negative alkali ions from alkali halides during 248-nm laser irradiation

Below laser fluences where a plasma is formed (the so-called plasma or plume formation threshold) a number of fundamental phenomena can occur where particles such as atomic and molecular ions, atoms and molecular neutrals, and electrons can be emitted. An understanding of such processes is necessary to develop predictive models for material removal from laser irradiated surfaces—at the foundation of laser etching, machining, and pulsed laser deposition. We have reported on a number of the mechanisms for such emission processes. Here, due to space limitations, we present a summary of our studies on the formation of negative alkali ions from single crystal KCl during exposure to pulsed 248-nm radiation at fluences well below the threshold for plasma formation. Despite the high electron affinities of the corresponding halogen atoms, negative halogen ions were not detected. Significantly, the positive and negative alkali ion distributions overlap strongly in time and space, consistent with K formation by the sequential attachment of two electrons to K⁺. Negative alkali ions are also observed under comparable conditions from LiF, NaCl, and KBr. In each material, the strong overlap between the positive and negative alkali ion distributions, and the lack of detected negative halogen ions, suggest that negative ion formation involves a similar mechanism.     

Shape resonances in slow electron scattering by aromatic molecules. I. Anthraquinone derivatives

A series of anthraquinone (C(14)O(2)H(8)) derivatives has been studied by means of electron capture negative ion mass spectrometry (ECNI-MS), photoelectron spectroscopy (PES), and AM1 quantum chemical calculations. Mean lifetimes of molecular negative ions M(-.) (MNI) have been measured. The mechanism of long-lived MNI formation in the epithermal energy region of incident electrons has been investigated. A simple model of a molecule (a spherical potential well with the repulsive centrifugal term) has been applied for the analysis of the energy dependence of cross sections at the first stage of the electron capture process. It has been shown that a temporary resonance of MNI at the energy approximately 0.5 eV corresponds to a shape resonance with lifetime 1-2.10(-13) s in the f-partial wave (l = 3) of the incident electron. The next resonant state of MNI at the energy approximately 1.7 eV has been associated with the electron excited Feshbach resonance (whose parent state is a triplet npi* transition). In all cases the initial electron state of the MNI relaxes into the ground state by means of a radiationless transition, and the final state of the MNI is a nuclear excited resonance with a lifetime measurable on the mass spectrometry timescale. Copyright 1999 John Wiley & Sons, Ltd.     

Internal conversion as the main stabilization mechanism for long-lived negative molecular ions

The temperature dependence of the mean lifetime of Ph-N=N-Ph^? azobenzene negative molecular ions on the captured electron energy is studied with a static mass spectrometer by the method of resonance electron capture. A family of respective experimental dependences is calculated accurate to 2–10%. It is shown that the molecular anions in the epithermal electron energy range can be stabilized through internal conversion, namely, a series of fast radiationless transitions without change in the multiplicity.     

Stability of negative ions near the surface of a solid

Stationary states of molecular negative ions (anions) near the surface of a solid are investigated. The lone electron is assumed to interact with a diatomic molecule and the surface of the solid. The energies of electron levels are determined by solving the 2D Schrödinger equation. It is shown that its stable solutions exist at distances from the surface greater than some critical distance, otherwise the electron is detached from the anion. In the case of attraction between the electron and the solid, the interaction potential between the anion and the solid appears to have the Lennard-Jones form and the ion is separated from the surface by some equilibrium distance.     

不同成分等离子体鞘层的玻姆判据

在一维平板鞘层中采用流体模型分别研究了不同成分无碰撞等离子体鞘层的玻姆判据.通过拟牛顿法数值模拟了含有电子、离子、负离子以及二次电子的等离子体鞘层玻姆判据.结果表明二次电子发射增加了鞘层离子马赫数的临界值,且器壁发射二次电子温度越高,离子马赫数临界值越小.负离子使离子马赫数临界值减小.而在含有二次电子和负离子的等离子体鞘层中,当负离子较少时,二次电子发射对离子马赫数临界值影响较大;当负离子增加时,离子马赫数的临界值则主要受负离子的影响. 关键词： 鞘层 等离子体 玻姆判据     

Analysis of cyclic boronated and trimethylsilylated phenolalkylamines by gas chromatography and electron impact mass spectrometry

The side chain of phenolalkylamines containing a bifunctional group was derivatized as the cyclic boronate, and then the residual phenolic group was trimethylsilylated. The resulting derivatives were single reaction products in each case, with good gas chromatographic properties and informative mass spectra to afford prominent molecular ions by gas chromatography with electron impact mass spectrometry (GC/EI-MS). The cyclic boronated-trimethylsilylated derivatives yielded the isotope pattern for boron ((10)B:(11)B =-1:4.2) and characteristic ions [M](+), [M - H](+), [M - CH(3)](+), [M - RBO](+), [M - TMSO](+), and [M - TMSO - C(6)H(5)](+) ions in the mass spectra. In order to distinguish between m- and p-phenolalkylamines, the mass spectra of the cyclic phenylboronated-trimethylsilylated (PBA-TMS) derivatives were compared with those of the trimethylsilylated (TMS) derivatives. The TMS derivatives of octopamine (p-) and norfenefrine (m-) showed identical mass spectra, while the PBA-TMS derivatives had mass spectra sufficiently different from one other to distinguish between the isomers. The most prominent ion of the PBA-TMS derivative is the [M - H](+) ion (m/z 310) for octopamine and the [M](+) ion (m/z 311) for norfenefrine. Copyright 1999 John Wiley & Sons, Ltd.     

Electron detachment from negative hydrogen and lithium ions by an ultrashort laser pulse

A model of electron detachment from negative ions is based on the approximation of instantaneous perturbation. A simple analytical representation for the ground state of the weakly bound electron is chosen to reproduce the radial distribution of electron density at any distance from the center of the ion. The probabilities of electron detachment from negative hydrogen and lithium ions are derived as functions of the transferred momentum of the laser field. The contribution of the inner shells of ions to the electron detachment is estimated. The momentum distribution of electrons in the final state is obtained. The effect of a pulse train on the total probability of detachment is considered for different pulse polarities. The conditions for the partial electron return to the initial state are revealed.     

Diamond surfaces: familiar and amazing

Diamond is the only wide band gap representative of the elemental semiconductors, with a crystal structure identical to its more common relatives silicon and germanium. On first glance one might also expect similar surface properties in terms of reconstructions, surface states, and surface band diagrams. In part, this expectation is indeed fulfilled, but diamond also exhibits a number of unusual and potentially very useful surface properties. Particularly when the surface dangling bonds are saturated by monovalent hydrogen atoms, (donor-like) surface states are removed from the gap, the electron affinity changes sign and becomes negative, and the material becomes susceptible to an unusual type of transfer doping where holes are injected by acceptors located at the surface instead of inside the host lattice. These surface acceptors can in the simplest case be adsorbed molecules conveniently chosen by their electron affinity, but they can also be solvated ions within atmospheric water layers or electrolytes in contact with the hydrogenated diamond surface. The understanding of those phenomena requires in fact concepts of surface science, semiconductor physics, and electrochemistry, which makes the diamond surface a true ‘interdisciplinary’ research topic. PACS 68.35.-p; 73.20.-r; 73.25.+i     

Tuning Photoinduced Intramolecular Electron Transfer by Electron Accepting and Donating Substituents in Oxazolones

The solvatochromic and spectral properties of oxazolone derivatives in various solvents were reported. Fluorescence spectra clearly showed positive and negative solvatochromism depending on substituents. The solvatochromic plots and quantum chemical computations at DFT-B3LYP/6-31?+?G(d,p) level were used to assess dipole moment changes between the ground and the first excited singlet-states. The electron accepting nitro substituent at the para-position increased the π-electron mobility, however, the 3,5-dinitro substituent decreased the π-electron mobility as a result of inverse accumulation of the electronic density as compared with that of its ground state. Experimental and computational studies proved that the photoinduced intramolecular electron transfer (PIET) is responsible for the observed solvatochromic effects. We demonstrate that PIET can be finely tailored by the position of the electron accepting and donating substituents in the phenyl ring of the oxazolone derivatives. We propose that the photoactive CPO derivatives are new molecular class of conjugated push-pull structures using azlactone moiety as the π-conjugated linker and may find applications in photovoltaic cells and light emitting diodes.