The kinetics of donor-acceptor pair transitions with strong phonon coupling in GaP

Donor-acceptor pair luminescence in GaP was studied by time-resolved spectroscopy, by measuring and analysing the integral band decay over many decades of intensity and time and by measuring and analysing the temperature dependence of the luminescence intensity. We report here the results obtained with some or all of these techniques for pairs involving deep as well as shallow centres. Those with a deep centre are: S_P-Si_P and Si_Ga-Si_P, in which the acceptor is the deep centre, and O_P-C_P and O_P-Zn_Ga, in which the donor is the deep centre. These pairs all have a broad, phonon-dominated luminescence band. The pairs involving shallow centres include Si_Ga-C_P, S_P-C_P and Te_P-C_P. Due to the different way of momentum conservation in these pairs, those involving a donor on a Ga-site have strong phonon co-operation and weak zero-phonon (ZP) transitions, whereas those with a donor on a P-site have strong ZP transitions.With time-resolved spectroscopy, well-resolved structure, due to a ZP pair band and its phonon replicas, is obtained for nearly all pairs. A comparison is made with the structure obtained by measuring in the stationary state at very low excitation densities. Some trends in the strength of phonon co-operation are noted. In the case of Si_Ga-C_P pairs, sharp replicas of ZP pair lines with a momentum-conserving phonon are also resolved.Using the integral band decay technique and results from time-resolved spectroscopy we have determined the transition probabilities for the total luminescence band as well as for the ZP band for nearly all pairs mentioned. The influence of incomplete saturation of the pairs during excitation with a focussed beam of an argon-ion laser is discussed and approximately corrected for. Extrapolated to zero pair separation, the total transition probability ranges from ∽ 10⁵s^-1 for Si_Ga-C_P pairs to ∽ 15 × 10⁵s^-1 for O_P-C_P and O_P-Zn_Ga pairs. The ZP probability ranges from ∽ 4 × 10³s^-1 for Si_Ga-C_P and Si_Ga-Si_P pairs to ∽ 4 × 10⁵s^-1 for S_P-C_P pairs. The transition probability for pairs in GaP is discussed in relation to the site occupied by the donor and the depth of the centres involved. The relatively high dope concentrations used in some cases, ∽ 1 to 2 × 10¹⁸cm^-3, are discussed briefly in relation to “concentration quenching”.The temperature dependence of the luminescence intensity of S_P-Si_P pairs is satisfactorily analysed with a simple linear model. The same model is applied to similar literature data on the S_P-C_P pair luminescence. Using in addition data on the average pair transition probability, trapping rate constants for hole capture by the Si_P and C_P acceptors were calculated to be ∽ 10^-9 cm³s^-1. Evidence is presented that the trapping rate constant for holes by the Zn_Ga-O_P complex is about 2 × 10^-9 cm³s^-1.     

Absorption spectra of C6H6 and C6D6 near 340 nm

The absorption spectra of C₆H₆ and C₆D₆ in the liquid phase have been studied near 340 nm. The absorption spectrophotometric mounting was a sequential double-beam attachment with linear response to energy on scanning of the spectrum before the exit slit and an electronic device which gives directly either the absorbance or the integrated absorbance of a transition and, consequently, its oscillator strength.The oscillator strength measured for the band of C₆H₆ is 8×10^?8, which corresponds to a dipole moment of 2.4×10^?3 Debye; this value is of the same order as a theoretical value calculated by Tsubomura and Mulliken (3.8×10^?3 Debye) for a transition between states ³F and ³A of an oxygen-benzene pair. This agreement corroborates the hypothetical existence of such a transition.The first vibrational band is at 28553 cm^?1 for C₆H₆; this band is not observed in the vapor or solid phase. It corresponds probably to the transition 0-0, which is considered in the literature to be near 29500 cm^?1. The isotopic shift measured for this first band is 164 cm^?1. The vibrational frequencies are, respectively, 910 cm^?1 for C₆H₆ and 889 cm^?1 for C₆D₆.     

A Sensitive Isotope Selective Nondispersive Infrared Spectrometer for 13CO2 and 12CO2 Concentration Measurements in Breath Samples

We present a nondispersive infrared spectrometer (NDIRS) for the measurement of the ¹³CO₂/¹²CO₂-ratio in breath samples. A commercial NDIR spectrometer for CO₂ concentration measurements in industrial process control was modified using two separate optical channels for the ¹³CO₂ and ¹²CO₂ detection. Cross interference due to overlapping absorption lines of both isotopic gases was successfully eliminated. The sensitivity of this device is ± 0.4‰ of the ¹³CO₂/¹²CO₂-ratio in a range of 2.5 to 5% of total CO₂. This is sufficient for biomedical applications. Our spectrometer is small in size, cheap and simple to operate and thus a true alternative to isotope ratio mass spectrometers (IRMS). Several biomedical applications with breath samples were demonstrated and were compared in very good agreement with IRMS.     

Raman spectroscopy of smithsonite

Raman spectroscopy at both 298 and 77 K has been used to study a series of selected natural smithsonites from different origins. An intense sharp band at 1092 cm⁻¹ is assigned to the CO₃²⁻ symmetric stretching vibration. Impurities of hydrozincite are identified by a band around 1060 cm⁻¹. An additional band at 1088 cm⁻¹ which is observed in the 298 K spectra but not in the 77 K spectra is attributed to a CO₃²⁻ hot band. Raman spectra of smithsonite show a single band in the 1405–1409 cm⁻¹ range assigned to the ν₃ (CO₃)²⁻ antisymmetric stretching mode. The observation of additional bands for the ν₃^g modes for some smithsonites is significant in that it shows distortion of the ZnO₆ octahedron. No ν₂ bending modes are observed for smithsonite. A single band at 730 cm⁻¹ is assigned to the ν₄ in phase bending mode. Multiple bands be attributed to the structural distortion are observed for the carbonate ν₄ in phase bending modes in the Raman spectrum of hydrozincite with bands at 733, 707 and 636 cm⁻¹. An intense band at 304 cm⁻¹ is attributed to the ZnO symmetric stretching vibration. Copyright © 2007 John Wiley & Sons, Ltd.     

作用表示波动方程中与面有关项

这篇短文的内容是:(i)对於量子场论中的i(δψ[σ])/(δσ(x))=V(x,σ)ψ[σ] 如何由寻常的“曲面上的薛定谔方程”导出,作一个较严格的讨论,以及 (ii)讨论上式中的V(x,σ)在什么条件下不包含有σ。我们证明了所需的条件是 (?L^I)/(?φ_μ) (?L^I)/(?φ_ν)=(?²L)/(?φ_μ?φ_ν)F(φ,φ_ρ),式中L,L^I代表总拉格朗日及作用拉格朗日,φ代表场量,φ_μ代表φ/x^μ,F(φ,φ_ρ)代表φ及φ_μ的一个任意函数。     

SCF-Xα studies of the electronic structures of C,Si and Ge oxides

SCF-Xα scattered wave cluster MO calculations are presented for the oxyanions CO₃^?2, CO₄^?4, SiO₃^?2, SiO₄^?4, SiO₆^?8, GeO₄^?4 and GeO₆^?8. A comparison of the calculations with available X-ray spectral data shows good agreement. The MO diagrams for CO₃^?2 and CO₄^?4 are found to be quite similar, suggesting that the four coordinate oxyanion is not inherently unstable; therefore a quartz polymorph of CO₂ may become stable at high pressure. On the other hand, the valence region width of SiO₃^?2 is much smaller than that of SiO₄^?4; thus the three-coordinate Si oxyanion is expected to be highly unstable. For the Ge oxyanions the average valence region width is substantially larger in the six-coordinate than in the four-coordinate form, suggesting a preference for octahedral coordination. These observations indicate that although the valence region width is only one factor affecting the total energy of a system, it is predictive of favored coordination number according to the following principle: a change from a higher to a lower coordination number oxyanion of a given cation, Mⁿ⁺, will be favorable if the lower coordinate form has a wider valence region at its equilibrium internuclear distance.     

Photodissociation spectroscopy of the chromium trimer ion

The electronic and geometric structures and photodissociation dynamics of the chromium trimer ion, Cr₃ ⁺, were investigated by photodissociation spectroscopy in the photon-energy range from 1.32 to 5.52 eV. The branching fractions of the product ions, Cr⁺ and Cr₂ ⁺, exhibit stepwise changes at the threshold energies for dissociation into Cr⁺+Cr₂, Cr+Cr₂ ⁺, Cr⁺+2Cr, and Cr^*+Cr₂ ⁺. It is noted that Cr₂ ⁺ is produced even above the threshold for atomization; the excess energy is redistributed to produce a fragment atom, Cr^*, in an excited state. The photodissociation action spectrum is well explained by a mixture of simulated spectra for two nearly-degenerate structural isomers identified by density functional calculations: those having a metastable C_2v structure and the most stable structure slightly distorted from the C_2v one. The barrier height between the two isomers which is lower than the zero-point energy suggests that Cr₃ ⁺ has an intrinsically floppy structure.     

氮化钽团簇阴离子Ta3N3-解离吸附N2中的15N/14N同位素交换研究

氮气分子的吸附和活化是固氮研究中的重要过程. 近年来过渡金属氮化物由于在合成氨催化研究中的优异表现而受到广泛关注. 但是,氮化物物种与氮气分子在高温下反应的微观机制仍然不清楚,而该过程对于认识反应中的温度效应以及缩小气相团簇体系和凝聚相体系间的差距具有重要意义. 本文使用质谱观测到氮化钽团簇阴离子Ta₃¹⁴N₃^-和¹⁵N₂在高温下(393∽593 K)发生¹⁵N/¹⁴N同位素交换而产生¹⁴N₂/¹⁵N¹⁴N. 结合理论计算,阐述了同位素交换反应的微观机理以及升高温度对于N₂在Ta₃N₃^-上解离吸附的促进作用. 而在对比实验体系Ta₃¹⁴N₄^-/¹⁵N₂中,观察到升高温度只能加速¹⁵N₂在吸附产物Ta₃¹⁴N₄¹⁵N₂^-上的脱附. 这是由于氮空位是氮化物物种活化氮气的必要条件,而Ta₃N₄^-中由于不存在氮空位因此不能活化和解离氮气. 该研究为合成氨中氮化物物种中氮空位的作用提供了重要信息并且为固氮研究中高效催化剂的设计提供了线索.     

Anisotropy of hexagonal ferrites with M,W and Y structures containing Fe3+ and Fe2+ as magnetic ions

The ferrimagnetic saturation moment and hexagonal anisotropy constant K₁ have been measured at 4K on a Zn₂Y single crystal and on polycrystalline BaFe²⁺₂W and SrFe²⁺₂W samples. The moment of Fe₂W is in agreement with a collinear spin coupling and with the known site occupation for the Fe²⁺ ions. The moment of Zn₂Y is 9% lower than the value for a collinear configuration.The uniaxial anisotropy of Fe²⁺ in hexagonal ferrites is discussed and compared with that of Co²⁺. No noticeable Fe²⁺ anisotropy is found in Fe₂W in contrast to LaM = LaFe²⁺Fe³⁺₁₁O₁₉, in which the Fe²⁺ anisotropy is strong. The difference is attributed to the symmetry difference of the sites occupied by the Fe²⁺ ions in both compounds. The current theory does not satisfactorily explain the anisotropy and quadrupole splitting of Fe²⁺ in LaM. From this it is concluded that admixing of ⁵E states and (or) the influence of a dynamical Jahn-Teller effect cannot be neglected.The dipole-dipole anisotropy is computed for the M, W and Y structure and some deviation from the literature data is found. Using these results, a mean anisotropy of 1.3 to 2.3 cm^?1 per Fe³⁺ ion is found for the three structures.     

Production ofH(2s) andH(2p) by electron detachment fromH − in collisions with nitrogen and oxygen

¹⁹⁹Hg Fourier Transform NMR studies of various solutions of diverse mercury salts in H₂O and D₂O or in the appropriate protonated and deuterated acids are reported for both Hg ₂ ⁺⁺ and Hg⁺⁺. In the different solutions investigated the¹⁹⁹Hg line positions depend on the concentration of the solution, on the solvents and their isotopic composition and on the temperature of the sample. A ratio of the Larmor frequency of¹⁹⁹Hg and of²H in a Hg(NO₃)₂ solution in dilute DNO₃ is given. Using this ratio and the measured chemical shifts, a ratio of the Larmor frequencies of¹⁹⁹Hg for infinite dilution relative to²H in pure D₂O is given. From this a g_I-factor for¹⁹⁹Hg is derived and compared with the g_I-factor of an optical pumping experiment. The resulting shielding constant is σ^* (hydrated¹⁹⁹Hg⁺⁺ versus¹⁹⁹Hg atom)=?24.32(5) · 10^?4. This yields an atomic reference scale for all measured NMR line shifts of mercury.     

Spectral holeburning and the Stark and Zeeman effects in SrF2:Sm2+

We have observed narrow (40 MHz) persistent spectral holeburning in SrF₂:Sm²⁺ for Sm²⁺ ions in perturbed cubic sites. The transition studied is ⁷F₀?⁵D₀ between the f-electron states. Stark effect measurements show a linear splitting with a coefficient of 0.006 MHz/V cm^-1 and the splitting pattern shows that the site has C_4V symmetry. The C_4V perturbation is very weak and leads to unresolved splittings of cubic T_1g levels of ～2 cm^-1. The nonlinear Zeeman effect was studied using holeburning and the coefficient of 1.04 Hz/G² shows that the predominant magnetic coupling is in the ground state as found recently for CaF₂:Sm²⁺.     

A hydrogen bonded complex C2H2…HBr isolated and characterized in the gas phase using pulsed-jet,Fourier transform microwave spectroscopy

A complex formed from ethyne and hydrogen bromide has been isolated and characterized by using a fast-mixing nozzle in conjunction with a pulsed-jet, Fourier transform microwave spectrometer. Any possible chemical reaction between the two components when mixed in the usual way was thereby precluded. The rotational constants A, B and C, the quartic centrifugal distortion constants δ_J, δ_Jk and δ_J and the Br nuclear hyperfine coupling constants X_aa and X_bb—X_cc (nuclear quadrupole) and M_bb (spin-rotation) were determined for each of the five isotopomers C₂H₂…H⁷⁹Br, C₂H₂…H⁸¹ Br, C₂H₂…D⁷⁹Br, C₂H₂…D⁸¹Br and C₂D₂…H⁷⁹Br. Interpretations of the spectroscopic constants show that the complex is planar and T shaped in the equilibrium conformation, with HCCH internuclear axis forming the cross of the T and the HBr internuclear axis lying along the C₂ axis of C₂H₂. The H of HBr is closer to the centre (?) of the π bond of ethyne, and therefore HBr is involved in a hydrogen bond to the π system, in which the distance of H from ? is r (?…H) = 2.469(1) A. The intermolecular stretching force constant is estimated as kσ = 5.38(2) Nm^?1 for the species involving a hydrogen bond (C₂H₂…H⁷⁹Br, C₂H₂…H⁸¹Br and C₂D₂…H⁷⁹Br) while this quantity increases to kσ = 5.68(2)Nm^?1 for those complexes bound through a deuterium bond (C₂H₂…D⁷⁹Br and C₂H₂…D⁷⁹Br). The opportunity is taken to consider similarities in the properties of complexes within the two series B…HBr and B…HC1 for a range of Lewis bases B, including B = C₂H₂. Some family relationships are identified in the two series.     

Charge transfer effects on the luminescent properties of Eu3+ in oxysulfides

Energy shifts of 4f⁶ states of Eu³⁺ in matrices, and phonon sidebands, linewidths and luminescence decay of Eu³⁺ in Ln₂O₂S (Ln=Lu, Y, Gd and La) have been studied. The charge transfer state (CTS) of Eu³⁺ is described by a model in which a hole is transferred from Eu³⁺ to ligands. Septet states obtained from the 4f⁷(⁸S) + hole configuration of CTS interact with the ⁷F term of the 4f⁶ configuration. This effect causes downward shifts of ⁷F_J states in matrices. Diffuse charge distributions for ⁷F_J states due to the mixing with CTS make the curvatuve of their adiabatic potential curves be smaller than that for ⁵D_J'. Such a difference in the potential curves between ⁷F_J and ⁵D_J' causes broadening of the absorption lines compared with the corresponding emission linewidths in Y₂O₂S. A dynamic Jahn-Teller model is proposed for the concentration-enhanced phonon sidebands accompanying 4f-4f transitions. The vibronics appear only in the excitation spectra and not in the emission spectra. Spectral distributions of the effective density of phonon states are obtained from the observed phonon sidebands for Ln₂O₂S: 5%Eu. The phonon spectra indicate delocalization of the 4f orbitals of Eu³⁺ with increasing the host-cation radius. The observed lifetimes of ⁵D₀ show a decrease in the same order due to decrease in the 4f-CTS mixing.     

Paramagnetic defects in manganese-doped lead tungstate

In manganese-doped PbWO₄ crystals, low-intensity signals of triclinic clusters Mn⁴⁺-V _O and Fe³⁺-V _Pb have been revealed in addition to signals of Mn²⁺ tetragonal centers. The Mn⁴⁺-V _O cluster is formed by a Mn⁴⁺ ion in the W⁶⁺ position, which is associated with a vacancy of the nearest neighbor O^2?ion, and the Fe³⁺-V _Pb cluster consists of a Fe³⁺ ion substituting for Pb²⁺ with a local compensation of by a lead vacancy. It has been shown that, in PbWO₄: Mn, there is also a small amount of Mn⁴⁺ tetragonal centers located in the Pb²⁺ position with a nonlocal compensation of an excess charge.     

Potential models and local mode vibrational eigenvalue calculations for acetylene

Two potential models for acetylene are developed and tested by comparison between variational calculations for the stretching vibrational term values and available spectroscopic data. The first model based on local bond potentials with harmonic interbond coupling gives root mean square deviations of 6 cm^?1 for C₂H₂ and 3 cm^?1 for C₂D₂. The second model is more ambitious, being designed to reproduce the dissociation characteristics of the molecules, and the calculated root mean square deviations from the experimental vibrational term values are larger, 32 cm^?1 for C₂H₂ and 24 cm^?1 for C₂D₂. The eigenvalue spectrum of C₂H₂ is shown to differ from that of C₂D₂ in showingmarked local mode features and this difference in behaviour is underlined by means of a correlation diagram. Finally it is shown how the known normal mode frequencies and anharmonic constants may be introduced into a simple model in order to predict the excited term values of C₂H₂, again with a root mean square deviation of 6 cm^?1.     

Optical absorption of s2-configuration ions in alkali halide crystals—III: The A band in Sn2+-doped crystals

The line shape of the A band in KCl:Sn²⁺, KBr:Sn²⁺, KI:Sn²⁺, RbCl:Sn²⁺ and RbBr:Sn²⁺ has been measured as a function of temperature between about 15 K and room temperature. As the spectra for all these systems are similar detailed results are presented only for RbCl: Sn²⁺, RbBr:Sn²⁺ and KBr: Sn²⁺. The experimental data resemble those of a previous study on KBr:In⁺ and KG:In⁺ in that the A band consists of two broad, overlapping components designated A₁ (the low energy component) and A₂. The separation between A₁ and A₂ is more marked at low temperature for Sn²⁺ than for In⁺, and no inversion of the ratio of the peak heights of A₁ and A₂ occurs as the temperature is varied, as was so for In⁺. Detailed calculations of the line shape are presented for KBr:Sn²⁺. These calculations show that one cannot account for the line shape purely in terms of the dynamical Jahn-Teller effect and that there is in addition a static splitting of the A state caused by a lowering in the symmetry of the crystal field.     

Electron hopping in Fe1−xCuxCr2S4 (0<x<0.5)

A theoretical expression for the line shape of the Mössbauer spectra in the presence of electron hopping between Fe²⁺ and Fe³⁺ is obtained by using a simple stochastic model. Analyses based upon this expression show that the origin of the complicated Mössbauer spectra observed in the magnetic semiconductors Fe_1?xCu_xCr₂S₄ (0<x<0.5) at 77 K is electron hopping between Fe⁺² and Fe³⁺ This hopping occurs at a rate of a few MHz. Quantitative estimates are given for some parameters; the isomer shifts, the internal magnetic fields, the quadrupole splittings and the proportions of Fe²⁺ and Fe³⁺. The valence distribution in this system is determined from the results. For example, the distribution Fe²⁺_0.69Fe³+_0.29Cu¹⁺_0.02Cr³⁺_1.72Cr²⁺_0.28S^2?₄ is obtained for x = 0.02. The existence of Cr²⁺ is concluded.     

On the dissociation of the ozone dication

A mechanism for the dissociation of the ozone dication formed by double ionisation of neutral O₃ is determined by ab initio calculations. The dication ground singlet state is found to have a linear equilibrium geometry that is stable with respect to dissociation to O⁺ and O₂⁺. However, at the Franck-Condon zone for formation of O₃²⁺ from the neutral molecule the singlet potential energy surface intersects with a dissociative triplet state. We propose that crossing to this dissociative triplet state can account for the absence of any long-lived O₃²⁺ ions in the electron-impact mass spectrum of ozone. Further calculations of the kinetic energy release for the fragmentation of O₃²⁺ to O⁺+O₂⁺ indicate that considerable vibrational excitation may be present in the O₂⁺ ion.     

Si中S0对、Se0对和Te0对的电子结构

利用紧束缚近似下的格林函数方法,讨论了Si中(S⁰)₂,(Se⁰)₂及(Te⁰)₂基态的能级和波函数。分析了几种不同的观点。(S⁰)₂,(Se⁰)₂及(Te⁰)₂均在禁带中引入一个对称性的A_1g能级和一个反对称性的A_2u能级,二者都是填满的。现有实验观测到的是较高的A_1g能级。从理论上指出了对称性的A_1g能级反而高于反对称性的能级的原因。而Si中(Se₂)⁺的g因子测量值和(S₂)⁺,(Se₂)⁺的ESR实验结果也支持本文的观点。 关键词：     

β-Na(Y1.5Na0.5)F6:Tm—A blue upconversion phosphor

A luminescent material β-Na(Y_1.5Na_0.5)F₆ doped with Tm³⁺ was synthesized by a solid-state reaction method for a steady phosphor of blue upconversion. Under the 671 nm laser excitation, the green emission band of 511 nm due to the ¹D₂→³H₅ transition is obtained for the first time, while the ultraviolet emission band is also observed at 368 nm, associated with the ¹D₂→³H₆ transition. Especially, a wide band of blue emissions is obtained at the wavelength region of 440-490 nm, originated mainly from the ¹D₂→³F₄ (450 nm) and ¹G₄→³H₆ (471-487 nm) transitions, which have potential application in tunable solid-state blue laser of Tm³⁺. The upconversion mechanism is explored in terms of the energy-level structures of Tm³⁺ ion and the power dependence of upconverted emission intensity, which is believed to be performed by excited-state absorption.