Local structure and triplet energy migration in p-dichlorobenzene-p-dibromobenzene solid solutions

Studies of the first triplet absorption and emission spectra of p-dichlorobenzene-p-dibromobenzene (DCB-DBB) mixed crystals agree generally with the data, indicating that this system forms solid solutions. However, the spectral properties are found to be very different from that of isotopically mixed crystals of comparable concentrations. The singlet-triplet absorption spectra of the DCB-DBB mixtures are generally broad and not amenable to detailed analysis indicating significant site dependent perturbations of the DCB and DBB triplet energies. Energy migration enhances emission from the lower energy sites and in consequence a red shift in the position of the emission (0,0) is observed, which is a maximum at equimolar concentrations. The emission bands are generally much broader than found for isotopically mixed crystals, indicating that the many types of sites in the DCB-DBB system remained uncoupled. This is a direct consequence of exciton trapping by inhomogeneous energy broadening caused by the site energy disorder being greater than the triplet exciton band width. Long-range triplet energy migration is not observed at DCB concentrations less than 99 per cent. This high limit is only expected for near one-dimension energy migration topologies. New structure observed at low DCB concentrations is tentatively interpreted as being due to the formation of DCB n-mers. The observed splittings indicate that the gas-to-crystal shift of the DCB T ₁ state increases (becomes more negative) by 11 cm^-1 when a neighbouring DBB molecule is replaced by DCB.     

Isotopic phonon effects in LaB(6)-LaB(6) do not possess cubic symmetry and show a non-random isotope distribution

The isotopic phonon effects in LaB(6) are investigated on the Raman spectra of a series of high-quality single crystals with systematically varied contents of (10)B and (11)B isotopes. A detailed group theoretical analysis enlightens the correlation between distortions of the B(6) octahedra and the splitting or broadening of phonon modes. It is evident that LaB(6) does not have cubic symmetry as assumed so far. A further symmetry reduction of the B(6) octahedra occurs in isotopically mixed crystals. There, the distribution of isotopes is not random as commonly assumed; the probability of associating equal isotopes increases with their mass decreasing.     

Barriers for pion-induced fission near A = 208

Measured fission cross sections for π⁺ and π^? beams of 150 MeV on isotopically separated targets near A=208 show a smooth dependence of the fission probability on the target mass, without any indication of the increased fission barriers expected for fission at low excitation near doubly magic ²⁰⁸Pb. Extraction of fission barriers from these data is attempted for a range of possible excitation energies, finding that these barriers are near 8 MeV near A=208, without much sensitivity to the assumed excitation energy.     

Submillimeter measurements of isotopes of nitric acid

The ground and low-lying vibrational states of nitric acid are observable with current instrumentation in the Earth’s thermal submillimeter atmospheric emission. Remote sensing continues to improve to higher sensitivity and future missions will allow these measurements with minimal integration time. Sensing of weaker spectral features will require signal averaging, and choices of spectral windows for these features will require knowledge of the higher vibrational states and rare isotopes of the strongly emitting species. Nearly comprehensive information on vibrational states and isotopically substituted species is now available from wide bandwidth scans of natural and isotopically enriched nitric acid. In this work, ground state rotational spectra of five isotopically substituted species of nitric acid are analyzed in the submillimeter spectral range. We present the Hamiltonian parameters necessary for prediction and identification of isotopic features across the nitric acid ground state rotational spectrum.     

用强场近似方法研究强激光场中H原子的电离

利用传统的强场近似方法和考虑Coulomb修正的强场近似方法,计算了H原子在激光场中的总电离几率及H原子在不同波长激光场中电离的能量谱,并将得到的能量谱与直接数值求解含时Schrödinger方程的结果进行了比较,结果发现：当激光波长较长时,考虑Coulomb 修正的强场近似方法得到的结果与数值求解含时Schrödinger方程的结果符合得较好。     

Energy degradation of electrons in krypton

The problem of energy degradation of electrons in krypton has been investigated using the Monte Carlo method. The results are presented as the probability distributions of the number of ionizations, the Fano factor, the mean energy per ion pair and the degradation spectra for source energies up to 4 keV.     

PtⅢ离子5d^8—5d^76P跃迁的极紫外光谱计算

本文运用多组态Hartree-Fock加相对论修正方法(MCHFR)计算了PtⅢ离子5d~8-5d~76p跃迁的光谱,得到了有关光谱数据如波长、振子强度和辐射跃迁几率,并就计算结果进行了简要分析.     

Experimental determination of the charge-transfer exciton band width in anthracene-PMDA crystal

The charge-transfer (CT) exciton is investigated on the reflection and luminescence spectra of isotopically mixed anthracene-PMDA crystals. The observed features are analyzed by the coherent potential approximation. It is concluded that the CT exciton in this crystal has the band width of about 100 cm^?1.     

Creation of bulk elementary excitations in superfluid helium-II by helium atomic beams at low temperatures

The experimental results of creating bulk elementary excitations (BEEs) in isotopically pure liquid helium-II by helium atomic beams at low temperatures ∼ 60 mK are presented. In the present experiment, BEE signals generated by ⁴He-atomic beams incident on the liquid free surface were detected by a bolometer positioned in the liquid helium-II. Some detected signals were very weak and depended on the heater power. Some examples of BEE detected signals are shown. Also, group velocities of the detected BEEs are evaluated and the threshold velocities of the helium atoms are discussed. The present experimental results demonstrate BEE creation, such as the third non-dispersive Zakharenko waves (supra-thermal phonons), with energies ∼17 K (the Cooper pairing phenomenon doubles the supra-thermal phonon energy E_k∼ 2 × 17 K∼34 K in order to fulfil the energy conservation law) in the positive roton branch of the BEE energy spectra by helium atomic beams with suitable energies ∼ 35 K, which perturb the liquid surface at incidence points similar to heaters.     

Temperature dependence in atom–surface scattering

It is shown that a straightforward measure of the temperature dependence of energy resolved atom–surface scattering spectra measured under classical conditions can be related to the strength of the surface corrugation. Using classical perturbation theory combined with a Langevin bath formalism for describing energy transfer, explicit expressions for the scattering probabilities are obtained for both two-dimensional, in-plane scattering and full three-dimensional scattering. For strong surface corrugations results expressed as analytic closed-form equations for the scattering probability are derived which demonstrate that the temperature dependence of the scattering probability weakens with increasing corrugation strength. The relationship to the inelastic rainbow is briefly discussed.     

Laser-induced emission from Te2, TeSe,TeS, and SeS in argon matrices

Laser-induced fluorescence spectra are reported for Te₂, TeSe, TeS, and SeS in argon matrices with both natural and isotopically enriched samples. From the total of nine band systems, two new electronic states are believed to have been identified for Te₂ and one each for TeSe and TeS.     

The origin and elimination of spurious peaks in threshold electron photoionization spectra

Autoionization electrons in threshold photoionization spectra are known to occur. The effect of such electrons on the interpretation of threshold electron spectra is discussed and a new method is described which enables one to discriminate between zero kinetic energy electrons and energetic electrons in photoionization experiments with little ambiguity. The method largely overcomes the main problem present in some previously described threshold electron studies; namely, the line-of-sight transmission of energetic electrons which gives rise to non-threshold electron peaks. A rejection ratio of 25 is readily obtained for 0.038 eV electrons compared with threshold (zero kinetic energy) electrons and the (small) transition probability for energetic electrons falls off more rapidly than for analysers previously described. Design parameters based on electron trajectory calculations are given for the analyser used, and photoionization results on argon are presented.     

Eu~(3+)掺杂碲酸盐闪烁玻璃的研究

用高温熔融法制备了Eu3+掺杂的碲酸盐闪烁玻璃。测试了Eu3+不同掺杂浓度玻璃样品的密度、差热特性、吸收、发射、激发光谱及X射线激发下的闪烁光谱。研究了不同Eu3+掺杂浓度对玻璃样品的密度、光谱性能的影响规律及掺杂离子的浓度猝灭效应。研究结果表明:Eu3+掺杂碲酸盐具有较大的密度和较强的闪烁发光,随着Eu3+浓度增加,由于Eu3+间的间距减小,共振能量转移几率增大,致使发光强度增强;但当掺杂到7mol%的高浓度时,会发生浓度猝灭效应。     

High-resolution LMN and LMM Auger spectra of Pd,Ag, In,Sn and Sb

Considerable interest in high-resolution Auger spectroscopy of the 4d metals has arisen because of the possibility of treating Auger spectroscopy as an excited state probe in order to extract new information regarding electronic structure. Auger transitions involving only core levels are interesting because current theories of line shapes and energies usually assume that the final core holes are either atomic or quasi-atomic. Comparison of the results of atomic calculations with experimental Auger spectra comprises a crucial test of the atomic theories.We present the results of high-resolution measurements of several high energy LMN and LMM Auger spectra of Pd, Ag, In, Sn and Sb excited with Ti Kα radiation. Assignments of the peaks are based upon energy and intensity considerations. We compare the experimental spectra with the results of atomic transition probability calculations, which indicates the reliability of such calculations as we proceed from open to closed 4d shell metals.     

The Rotational Spectra, Isotopically Independent Parameters, and Interatomic Potentials for the X(1)(2)Pi(3/2) and X(2)(2)Pi(1/2) States of BrO

Observations of the rotational spectrum of BrO have been extended to include vibrational levels up to v = 8 in the X(1)(2)Pi(3/2) and v = 7 in the X(2)(2)Pi(1/2) states. The rotational spectra of isotopically enriched Br(18)O, X(1), v = 0, 1 and X(2), v = 0 have been observed as well. The spectra of all four isotopic species have been fit to a Hamiltonian in which the parameters have fixed isotopic ratios. An extensive set of isotopically independent parameters has been determined. Interatomic potentials have been derived for both the X(1) and X(2) states. The hyperfine constants and their vibrational dependencies have been determined more precisely and several of them have been determined for the first time. These are interpreted in terms of the electronic structure of the molecule. The isotope relations among the constants have provided a means of decorrelating the electron spin-rotation constant gamma from the fine-structure centrifugal distortion constant, A(D), and have allowed the first determination of an effective value for gamma. Copyright 2001 Academic Press.     

Creation of bulk elementary excitations in superfluid helium-II by helium atomic beams at low temperatures

The experimental results of creating bulk elementary excitations (BEEs) in isotopically pure liquid helium-II by helium atomic beams at low temperatures ～ 60 mK are presented. In the present experiment, BEE signals generated by ⁴He-atomic beams incident on the liquid free surface were detected by a bolometer positioned in the liquid helium-II. Some detected signals were very weak and depended on the heater power. Some examples of BEE detected signals are shown. Also, group velocities of the detected BEEs are evaluated and the threshold velocities of the helium atoms are discussed. The present experimental results demonstrate BEE creation, such as the third non-dispersive Zakharenko waves (supra-thermal phonons), with energies ～17 K (the Cooper pairing phenomenon doubles the supra-thermal phonon energy E _k ～ 2 × 17 K～34 K in order to fulfil the energy conservation law) in the positive roton branch of the BEE energy spectra by helium atomic beams with suitable energies ～ 35 K, which perturb the liquid surface at incidence points similar to heaters.     

Soliton and rogue wave statistics in supercontinuum generation in photonic crystal fibre with two zero dispersion wavelengths

Stochastic numerical simulations are used to study the statistical properties of supercontinuum spectra generated in photonic crystal fibre with two zero dispersion wavelengths. For picosecond pulse excitation, we examine how the statistical properties of solitons generated on the long wavelength edge of the supercontinuum (``optical rogue waves") are modified by energy transfer to dispersive waves across the second zero dispersion wavelength. The soliton statistics (characterized in terms of peak power, wavelength and pulse duration) are shown to be strongly modified by the mechanism of dispersive wave generation, with the detailed form of the probability distribution depending strongly on input pulse energy.     

Electron transmission through organized organic thin films studied by discrete initial electron kinetic energies

Synchrotron radiation (SR) pulses are used to eject electrons from a gold substrate covered with organized organic thin films (OOTF) in order to investigate their transmission probability through the OOTF as a function of the electron initial kinetic energy. By variation of the SR photon energy within a few eV above the Au-4f binding energy levels we controlled the initial kinetic energy of the substrate electrons. The observed oscillations in the transmission probability for porphyrin-based films as a function of the kinetic energy is argued to be due to effects of band structure above the vacuum level in the well-ordered molecular adsorbate. We also present valence photoemission spectra (PES) of different type OOTF and demonstrate how their coverage of the substrate affects the PES. Received 24 July 1998     

Isotope shifts in spectra of molecular liquids

In the IR absorption spectra of low-temperature molecular liquids, we have observed anomalously large isotope shifts of frequencies of vibrational bands that are strong in the dipole absorption. The same effect has also been observed in their Raman spectra. At the same time, in the spectra of cryosolutions, the isotope shifts of the same bands coincide with a high accuracy (±(0.1–0.5) cm^–1) with the shifts that are observed in the spectra of the gas phase. The difference between the spectra of examined low-temperature systems is caused by the occurrence of resonant dipole–dipole interactions between spectrally active identical molecules. The calculation of the band contour in the spectrum of liquid freon that we have performed in this work taking into account the resonant interaction between states of simultaneous transitions in isotopically substituted molecules can explain this effect.     

Improved sample preparation of glyphosate and methylphosphonic acid by EPA method 6800A and time-of-flight mass spectrometry using novel solid-phase extraction

The employment of chemical weapons by rogue states and/or terrorist organizations is an ongoing concern in the United States. The quantitative analysis of nerve agents must be rapid and reliable for use in the private and public sectors. Current methods describe a tedious and time-consuming derivatization for gas chromatography-mass spectrometry and liquid chromatography in tandem with mass spectrometry. Two solid-phase extraction (SPE) techniques for the analysis of glyphosate and methylphosphonic acid are described with the utilization of isotopically enriched analytes for quantitation via atmospheric pressure chemical ionization-quadrupole time-of-flight mass spectrometry (APCI-Q-TOF-MS) that does not require derivatization. Solid-phase extraction-isotope dilution mass spectrometry (SPE-IDMS) involves pre-equilibration of a naturally occurring sample with an isotopically enriched standard. The second extraction method, i-Spike, involves loading an isotopically enriched standard onto the SPE column before the naturally occurring sample. The sample and the spike are then co-eluted from the column enabling precise and accurate quantitation via IDMS. The SPE methods in conjunction with IDMS eliminate concerns of incomplete elution, matrix and sorbent effects, and MS drift. For accurate quantitation with IDMS, the isotopic contribution of all atoms in the target molecule must be statistically taken into account. This paper describes two newly developed sample preparation techniques for the analysis of nerve agent surrogates in drinking water as well as statistical probability analysis for proper molecular IDMS. The methods described in this paper demonstrate accurate molecular IDMS using APCI-Q-TOF-MS with limits of quantitation as low as 0.400 mg/kg for glyphosate and 0.031 mg/kg for methylphosphonic acid.