Letters to the editor

Abstract

Optical absorption spectra of TeO₂ crystals, irradiated at room temperature by up to 2·10¹⁸ cm^?2 10-MeV electrons and subsequently annealed to 575K, are studied. The dependence of Urbach absorption edge parameters in TeO₂ on the electron beam fluence is discussed. The irradiation-induced near-edge broad (2.5–3.5eV) absorption band is shown to be related to oxygen vacancies, annealing at 475–525K.     

Measurements of total cross sections for positron-K and-Rb scattering

A modification of the apparatus that we have been using to measure absolute total cross sections (Q _T′s) for positron and electron scattering by alkali metal atoms has enabled us to more easily obtainQ _T′s at low energies (<10 eV). Our positron-K and-RbQ _T measurements now extend from 1 to 98 eV and we have made the correspondingQ _T measurements for electrons in the same system using the same technique (a beam transmission technique). Our measured positron-K and-RbQ _T values show a peak in the vicinity of 6 eV and decrease substantially as the positron energy is reduced below 6 eV, in sharp contrast to the results obtained in recent 5-state close-coupling approximation calculations. At higher energies (above 10 eV), we have found that the same calculations are in quite good agreement with our measured positron-K and-RbQ _T′s. Our measurements of the correspondingQ _T′s for electrons below 10 eV do not show a peak, but rather continue to increase as the energy is decreased.     

Polarized Fluorescence of Complex Molecules Being Excited by Low-Energy Electrons

Polarization of the fluorescence of the vapors of anthracene, perylene, 1,4-di(2,5-phenyloxazolyl)benzene (POPOP), and 2-phenyl-5-(4-biphenylyl)oxazole (BPO) upon excitation by a beam of monokinetic electrons with energy varying in the 5–300-eV range has been found. The electrical vector of radiation has a higher value in the direction perpendicular to the direction of the electron beam. For the substances studied, maxima of fluorescence polarization are observed that approximately coincide in position with the maxima of the excitation function. The maximum value of the fluorescence polarization degree of POPOP does not exceed 3.8%.     

Spectral‐Luminescent Properties of Oxazoles and Oxadiazoles in a Gas Phase on Excitation by Electrons

The energyloss spectra of electrons, fluorescence excitation functions, and the fluorescence spectra on excitation of the vapors of a number of oxazoles and oxadiazoles by monokinetic beams of electrons of various energies are determined. In contrast to optical absorption spectra, in the energyloss spectra of a number of studied substances a band associated with the S ₀–T ₁ singlettriplet transition is observed. The –^*type transitions are fixed up to S ₀–S ₅ on excitation of molecules by highenergy electrons, including the region of vacuum ultraviolet. The cross sections of elastic and inelastic collisions of electrons of different energies with POPOP molecules have been measured. The dependences obtained differ substantially from those calculated in the Born approximation. The cross section of elastic scattering is in a rather good correspondence with the geometric section of the molecule.     

Role of charge-transfer complexes in oxygen quenching of excited states of anthracene derivatives in the gas phase

Oxygen quenching of excited triplet and singlet states of gas-phase anthracene and its derivatives that have similar energies of the lower triplet levels but widely different oxidation potentials (0.44 < E_ox < 1.89 V) was studied. Quenching rate constants for singlet (k_S^O2) and triplet (k_T^O2) states in addition to the fraction of oxygen-quenched singlet and triplet states q_{S 1}(T₁^O2 were determined from the decay rates, fluorescence intensities, and delayed fluorescence as functions of oxygen pressure. It was found that k_S^O2 values vary from 2·10⁴ (9,10-dicyanoanthracene) to 1.2·10⁷ sec⁻¹·torr⁻¹ (anthracene, 9-methylanthracene, 2-aminoanthracene) and k_S^O2 values from 5·10² to 1·10⁵ sec⁻¹·torr⁻¹. The k_S^O2 values for anthracene, 9-methylanthracene, and 2-aminoanthracene, which have fast rates of interconversion from S₁ to T₁, are close to the rate constants for gas-kinetic collisions and are independent of the oxidation potentials (E_ox). The quenching rate constants k_S^O2 for the other anthracene derivatives and k_T^O2 for all studied compounds decrease with increasing free energy of electron transfer ΔG_ET, which indicates the important role of charge-transfer interactions in the oxygen quenching of singlet S_1- and triplet T₁ states. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 36–42, January–February, 2008.     

Temperature dependence of the radiation-stimulated conductivity of CsI crystals upon picosecond excitation by electron beams

The temperature dependence of the pulse conductivity for CsI crystals upon excitation with an electron beam (0.2 MeV, 50 ps, 400 A/cm²) at a time resolution of 150 ps is investigated. Under experimental conditions, the time of bimolecular recombination of electrons and holes (V _k centers) is directly measured in the temperature range 100–300 K. This made it possible to calculate the temperature dependence of the effective recombination cross section S(T)=7.9×10^?8 T² cm². The temperature dependence of the conductivity σ(T) is interpreted within the model of the separation of genetically bound electron-hole pairs. The activation energy of this process is found to be E _G =0.07 eV.     

Excitation of lowest electronic states of the uracil molecule by slow electrons

The excitation of lowest electronic states of the uracil molecule in the gas phase has been studied by electron energy loss spectroscopy. Along with excitation of lowest singlet states, excitation of two lowest triplet states at 3.75 and 4.76 eV (±0.05 eV) and vibrational excitation of the molecule in two resonant ranges (1?C2 and 3?C4 eV) have been observed for the first time. The peak of the excitation band related to the lowest singlet state (5.50 eV) is found to be blueshifted by 0.4 eV in comparison with the optical absorption spectroscopy data. The threshold excitation spectra have been measured for the first time, with detection of electrons inelastically scattered by an angle of 180°. These spectra exhibit clear separation of the 5.50-eV-wide band into two bands, which are due to the excitation of the triplet 1³ A?? and singlet 1¹ A?? states.     

外场作用下蒽分子的激发特性研究

蒽(anthracene)具有良好的热稳定性以及较高的荧光量子产率的优点, 是最早用于研究有机发光器件(organic light-emitting device, OLED)的材料之一. 在本文中, 主要利用量子化学方法研究了不同外电场对蒽分子激发特性的影响规律. 首先采用密度泛函理论(density functional theory, DFT)在6-311G(d, p)基组水平上对蒽分子基态结构进行优化, 基于稳定基态结构, 利用含时密度泛函(time-dependent density functional theory, TDDFT)以及同一基组水平, 计算出蒽分子的前十个激发态的激发能、跃迁偶极矩、振子强度和紫外吸收光谱等数据. 然后以密度泛函B3P86方法优化出的不同外电场下蒽分子基态结构为基础, 使用TDDFT方法研究了不同外电场对蒽分子前线轨道能级和激发特性的影响规律. 结果显示, 无场时蒽分子在紫外区域234.50 nm处有一个较强的吸收峰, 对应基态电子跃迁至第5激发态吸收光子波长; 在外电场作用下, 蒽分子电子由基态跃迁到激发态的各项光谱参数均有显著变化, 加场后蒽分子的吸收光谱发生了红移, 由紫外波段移向了紫外–可见光波段, 与实验值相符合. 分子前线轨道的计算结果也表明蒽分子的最高占据轨道(highest occupied molecular orbital, HOMO)和最低未占据轨道(lowest unoccupied molecular orbital, LUMO)能量差值在不同电场下存在差异. 关键词： 蒽 外电场 激发特性     

Resonance scattering of electrons from orientated O2 physisorbed on graphite

We have studied inelastic electron scattering from a saturated monolayer of O₂ physisorbed on graphite at 25K. The cross-section for excitation of the v = 0–1 vibrational transition in O₂ peaks at 8.5–9eV, and is attributed to the ⁴Σ_u negative ion resonance. The angular distribution of electrons inelastically ejected out of the resonance orbital has been measured, and is found to peak at 15° from the normal to the crystal for several different incident electron beam angles, in accord with the theory of resonant electron scattering by an orientated molecule. We discuss the implications of this measurement for a determination of the orientation of the O₂ molecule on the surface, taking account of possible multiple scattering effects.     

Spectral characteristics of heterocyclic compounds with a chain structure, cooled in an ultrasonic jet

We have recorded the fluorescence excitation spectra of three heterocyclic compounds with a chain structure [BPO (2-phenyl-5-(4-diphenylyl)oxazole), POPOP (1,4-di[2-(5-phenyloxazolyl)]benzene, and TOPOT (1,4-di[2-(5-n-tolyloxazolyl)]benzene] and the fluorescence spectra of POPOP, under conditions where the molecules were cooled in an ultrasonic helium jet. A line structure is observed in the spectra of POPOP and TOPOT; for the BPO molecules, whose configuration changes considerably during electronic excitation, vibrational structure is apparent only in the low-frequency region of the excitation spectrum, and a diffuse spectrum is recorded starting from ν ₀ ⁰ + 200 cm⁻¹. For all the compounds, in the spectra we recorded vibrations with frequencies up to 100 cm⁻¹, arising due to the flexibility of the molecular structure. The rotational contours of the lines for the electronic and vibronic transitions of the POPOP molecules (T_rot = 10.5 K) and TOPOT molecules (T_rot = 15 K) are structureless and bell-shaped. The degree of polarization of the fluorescence P_fl for the jet-cooled POPOP molecules for excitation of vibrations along the absorption band up to 2000 cm⁻¹ above ν ₀ ⁰ is practically constant (∼8.4%) and matches P_fl for high-temperature vapors. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 728–734, November–December, 2006.     

紫外光诱导光电子发射负离子源的阈值光电子成像仪设计 (cited: 2)

设计了一套紧凑的光电子成像装置,它包括解离式光电子贴附负离子源、垂直安装的高分辨阈值光电子速度成像装置和线性飞行时间质谱仪．紫外光辐射金属表面诱导低能光电子发射,再通过低能电子贴附超声分子束产生高强度和冷的负离子源．结合这种负离子源和飞行时间质谱-光电子成像仪装置,仪器的质量分辨能达到200左右,能量分辨优于3%(即对1 eV动能的电子,分辨达到30 meV)．此外,使用该实验装置获得了CH₃S^-和S₂^-在611.46 nm下的低能阈值光电子成像结果．同时得到了CH₃S和S₂的更精确的电子亲和势分别为1.8626±0.0020和1.6744±0.0035 eV．初步的结果证明了该装置对研究阈值光电子成像精确测量光电子亲和势非常有效     

Spectral‐Luminescence Characteristics of Polyphenyls and Polyacenes in the Gas Phase in Electron‐Beam Excitation

The spectra of electronenergy loss, excitation functions, and fluorescence spectra in excitation of the vapor of polyphenyls and polyacenes by electron beams of different energies are determined. The influence of successive complication of the molecules under study on these spectralluminescence characteristics is tracked. Unlike the optical absorption spectra, in the spectra of electronenergy loss of all the substances studied one observes a band which is related to the singlettriplet transition S ₀–T ₁. The transitions up to S ₀–S ₅ are recorded in excitation of the molecules by highenergy electrons, including the region of vacuum ultraviolet. From the functions of fluorescence excitation the authors have determined the excitation thresholds that correlate with the energies of the S ₁ levels, except for pyrene in which the S ₀–S ₁ transition is forbidden and does not show up not only in photon excitation but also in electronbeam excitation, although the intercombination forbiddenness in the latter case is removed and the S ₀–T ₁ band is observed.     

Electron energy loss spectra of dye vapors

Electron energy loss studies of POPOP andp-terphenyl in the vapor phase at an incident electron energy of 25 eV have been performed. The spectra covering an energy loss between 0 and 9 eV revealed a considerable initial triplet population under electron impact excitation. The implications for electron-beam pumped vapor phase dye lasers are discussed.     

Fragmentation of the POPOP molecule by electron-impact ionization

Single and dissociative ionizations of the POPOP molecule by electron impact in the gas phase are studied using mass spectroscopy. Fragmentation pathways of the molecule are proposed taking into account the common system of conjugated π-electrons and heteroatoms in the POPOP molecule. The appearance thresholds for certain fragments of the molecule are determined based on experimentally measured ionization cross sections as functions of the ionizing electron energy. An ion with m/z = 144 [C₉H₆ON]⁺ that is complementary to a fragment with m/z = 220 [C₁₃H₁₀ON]⁺ (present in the NIST mass spectrum database) is found for the first time in the mass spectrum of POPOP. Its appearance threshold is determined (E_ap = 9.48 eV). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 482–489, July–August, 2008.     

Excitation of the 3p3Πu level of H2 by electron impact; pressure effects

The excitation cross-section of the 3p³Π_u level of H₂ has been measured for electrons from energy threshold to 100 eV. We compare the intensities of the emitted lines to the Balmer lines whose excitation cross-sections from H₂ are known. The effects of dissociation, cascade, polarisation and pressure are discussed. The maximum excitation cross-section is found to be 3·30 × 10^-18 cm² ± 50% at 22·5 eV.     

Photophysical parameters for potential vapour-phase dye-laser media

The fundamental photophysical parameters of the organic scintillators, anthracene, 9, 10 dimethyl antracene (DMA), 9, 10 diphenyl anthracene (DPA), 2-(1-napthyl)-5-phenyloxazole (α-NPO) and 2, 2′-p-phenyl bis (5-phenyloxazole) (POPOP), were investigated in the liquid and vapour phases. Their ground state, triplet-triplet and fluorescence spectra were determined and accurate extinction coefficients obtained. Photodecomposition of POPOP vapour under 337 nm excitation was investigated in detail and a photodecomposition quantum yield of 1.1×10⁻² obtained at 568 K. The POPOP triplet state in the vapour phase is quenched by the addition of 1, 3, 5, 7 cyclo-octatetraene and a quenching rate constant of 2.9×10¹⁰ M⁻¹ s⁻¹ was determined.     

Excitation transfer into bound and continuum states investigated by optical and electron spectroscopy

We present energy spectra of electrons formed in the reaction of He(2³ S, 2¹ S) with NO₂ which have significantly improved counting statistics and resolution compared to earlier work. Further, we show spectra of the fluorescence light emitted in these reactions. The data are recorded in the same molecular beam apparatus as the electron spectra. For the metastable singlet state He(2¹ S) the spectra have not been measured before. We find that in addition to ionization excitation transfer takes place into Rydberg states of NO₂**. Subsequently, the highly excited NO₂** molecules dissociate into NO and atomic O* Rydberg atoms.     

The dissociative excitation of singlet levels of the singly charged lanthanum ion in collisions of electrons with lanthanum bromide molecules

The method of extended crossing beams was used to study inelastic collisions of slow electrons with LaBr₃ molecules. Dissociative excitation caused the appearance of spectral lines of the singly charged lanthanum ion. 38 dissociative excitation cross sections of LaII spectral lines (upper singlet levels) were studied at a 100 eV exciting electron energy. Three optical excitation functions were recorded over the electron energy range 0–100 eV. The cross sections obtained are compared with the data on dissociative excitation cross sections of the LaCl₃ molecule.     

Inner shell excitation of CH 3F,CH 3Cl,CH 3Br and CH 3I by 2.5 keV electron impact

Small angle inelastic scattering of 2.5 keV electrons was used to study inner shell excitation in the methyl halides at energy transfers between 50 and 700 eV. Discrete peaks due to the excitation of carbon K, fluorine K, chlorine L, bromine M_{4, 5} and iodine N _{4, 5} electrons were observed. Correlations through the methyl halide series were used to aid in the assignment of features in the carbon K-shell spectra. A comparison of halogen inner-shell excitation structures with the carbon K-shell excitation structure in the same molecule allowed a complete assignment of all spectral features. The assignments proposed involve promotions of inner shell electrons to unoccupied valence and Rydberg orbitals. On the basis of our assignments of the chlorine L- and carbon K-shell electron energy loss spectra of CH ₃Cl we propose an alternate assignment of the previously reported CH ₃Cl chlorine K-shell photoabsorption spectrum.     

Spectral-Luminescence Characteristics of Carbazole, Dibenzofuran, and Dinaphthofuran in the Gas Phase in Excitation by Electrons and Photons

The spectra of electron-energy loss, the excitation functions, and the fluorescence spectra in excitation of carbazole, dibenzofuran, and dinaphthofuran by monoenergetic beams of electrons of different energies are determined. The singlet-triplet transitions S ₀–T ₁ and the singlet-singlet transitions up to S ₀–S ₇ are recorded, which covers the region 2–11 eV. In the spectra of electron-energy loss, bands that refer to the n^ast and ^* transitions are identified. The replacement of the heteroatom of nitrogen by the atom of oxygen in the five-membered ring has no substantial effect on the spectra of electron-energy loss.