The valence ionization potentials (IP's) of cyclopentadiene and 1-sila-cyclopentadiene-(2,4) are studied by an ab initio many-body approach which includes the effect of electron correlation and reorganization beyond the Hartree-Fock approximation. The Hartree-Fock approximation gives the correct ordering of the IP's for cyclopentadiene but this ordering does not agree with the results of the previous experimental and theoretical studies. The ordering is 1a2(π), 2b1(π), 4b2, 6a1, 5a1, 3b2, 1b1 (π), 4a1, 2b2, 3a1. For sila-cyclopentadiene the ordering of the IP's is: 1a2(π), 4b2, 2b1(π), 6a1, 1b1(π), 5a1, 3b2, 4a1, 3a1, 2b2. The Hartree-Fock approximation is found to be incorrect with respect to the ordering of the 4b2 and 2b1(π) IP's. A number of one-electron properties are calculated in the one-particle approximation and compared with the available experimental data. 相似文献
The vertical valence ionization potentials of cyclopropane, ethylene oxide and ethylene imine are calculated by a many-body Green's function method. For C3H6 the ordering of the ionization potentials is 2e(), 1e(), 2a1(), 1a2(), 1e(). The assignment of the 2a1 and the 1a2 ionization potentials which has been controversial is thus clarified. The ordering is in agreement with the result obtained via Koopmans' theorem. For ethylene oxide and ethylene imine Koopmans' theorem fails in predicting the correct order of ionic states. For C2H4O the ordering of the ionization potentials is 2b1(), 4a1, 1a2(), 2b2,3a1, 1b1(), 1b2, 2a1 and for C2H5N 6a, 5a, 3a, 2a, 4a, 3a, 1a, 2a. The agreement of the computed ionization potentials with the experimental values is very satisfactory. 相似文献
We analytically investigate the effect of an external mirror on the stability of an injected semiconductor laser, the latter treated as injected damped oscillators. In the studied configuration, the injected semiconductor laser with an external mirror is under the influence of a chaotic oscillating optical signal that is generated by a similar semiconductor master laser. We derive our results in terms of the damping rate and resonance frequency. We show that the external mirror can eliminate the unstable modes of the injected laser at low frequencies. Furthermore, the mirror can enhance the damping of the oscillation modes of the injected semiconductor laser; consequently, the driven response of the injected laser may have a broad spectrum, even wider than that of the chaotic driving signal. We also show results for the bandwidths of the injection amplitude and phase increment as functions of the injection rate and feedback strength of the external mirror. In addition, we use bifurcation and time-series curves to describe the dynamical behavior of the injected laser. We identify the feedback strength of injected laser, relative to that of the master laser, which induces synchronization between the injected-laser oscillation modes and the master laser. 相似文献
Amplification of femtosecond pulses at 1.56 microm based on noncollinear parametric chirped pulse amplification in a potassium titanyl arsenate (KTA) crystal with pumping at 1.05 microm is reported. The 100 fs pulses of an erbium fiber laser are parametrically amplified while synchronously pumped by an amplified mode-locked Nd:YLF laser. This amplifier has a saturated gain of 65 dB with 30% conversion efficiency and has produced 160 fs pulses with peak powers of up to 0.75 GW. The system produced 380 mW before compression and can be readily scaled to the multiwatt range with bandwidths to support sub-100 fs pulses. 相似文献
Solutions are presented herein of some contact problems connected with the torsion of a composite half-space. In the general case the problem of the torsion of a composite elastic half-space is examined by means of the rotation of a stiff finite cylinder welded into a vertical recess of this half-space. Moreover, the following particular problems on the torsion of such a half-space are considered.
1. 1) A composite half-space with a vertical elastic infinite core, twisted by means of the rotation of a stiff stamp affixed to the upper endplate of the elastic core.
2. 2) A half-space with a vertical cylindrical infinite hole, twisted by means of the rotation of a stiff finite cylinder welded into the upper part of this hole.
In the general case the solution of the problem reduces to the solution of an integral equation of the second kind on a half-line. The question of the solvability of this fundamental integral equation is investigated, and it is shown that its solution may be constructed by successive approximations.
Let us note that the problem of the torsion of a homogeneous half space and of an elastic layer by means of rotation of a stiff stamp has been considered by Rostovtsev [1], Reissner and Sagoci [2], Ufliand [3], Florence [4], Grilitskii [5] and others.
The problem of the torsion of a circular cylindrical rod and the half-space welded to it which are subject to a torque applied to the free endface of the rod has been considered by Grilitskii and Kizyma[6].
The torsion of an elastic half-space with a vertical cylindrical inclusion of some other material by the rotation of a stiff stamp on the surface of this half-space has been considered in [7], wherein it has been assumed that the stamp is symmetrically disposed relative to the axis of the inclusion and lies simultaneously on both materials. 相似文献
Hole-doped rare-earth manganite La0.7Ca0.3MnO3 and the electron-doped manganite La0.7Ce0.3MnO3 both show a metal-insulator transition around 250 K associated with a ferromagnetic transition and colossal magnetoresistance.
In an earlier publication we have reported the rectifying characteristic of La0.7Ca0.3MnO3/SrTiO3/La0.7Ce0.3MnO3 tunnel junction at room temperature, showing that it is possible to fabricate a diode out of the polaronic insulator regime
of doped manganites. Here we report the magneto-transport properties of such a tunnel junction above and below the metal-insulator
transition. We show, from the large positive magnetoresistance of the tunnel junction at low temperature, that La0.7Ce0.3MnO3 could be a minority spin carrier ferromagnet. The implication of this observation is discussed. 相似文献
A concept of fluorescent metal ion sensing with an easily tunable emission wavelength is presented and its principle demonstrated by detection of Cu(2+). A fluorescein dye was chemically modified with a metal chelating group and then attached to the terminus of ss-DNA. This was combined with a complementary ss-DNA modified with another fluorescent dye (ATTO 590), emitting at a longer wavelength. In the assembled duplex, fluorescence resonance energy transfer (FRET) between the fluorescein donor (excited at 470 nm) and the ATTO 590 acceptor (emitting at 624 nm) is observed. Proper positioning within the rigid DNA double helix prevents intramolecular contact quenching of the two dyes. Coordination of paramagnetic Cu(2+) ions by the chelating unit of the sensor results in direct fluorescence quenching of the fluorescein dye and indirect (by loss of FRET) quenching of the ATTO 590 emission at 624 nm. As a result, emission of the acceptor dye can be used for monitoring of the concentration of Cu(2+), with a 20 nM detection limit. The emission wavelength is readily tuned by replacement of ATTO-DNA by other commercially available DNA-acceptor dye conjugates. Fluorescent metal ion sensors emitting at >600 nm are very rare. The possibility of tuning the emission wavelength is important with respect to the optimization of this sensor type for application to biological samples, which usually show broad autofluorescence at <550 nm. 相似文献
A liquid chromatographic/mass spectrometric assay with atmospheric pressure chemical ionization (LC/APCI-MS) is presented for fast and reliable screening and identification and also for precise and sensitive quantification in plasma of the 23 benzodiazepines alprazolam, bromazepam, brotizolam, camazepam, chlordiazepoxide, clobazam, clonazepam, diazepam, flunitrazepam, flurazepam, desalkylflurazepam, lorazepam, lormetazepam, medazepam, metaclazepam, midazolam, nitrazepam, nordazepam, oxazepam, prazepam, temazepam and tetrazepam, triazolam, their antagonist flumazenil and the benzodiazepine BZ1 (omega 1) receptor agonists zaleplone, zolpidem and zopiclone. It allows confirmation of the diagnosis of an overdose situation and monitoring of psychiatric patients' compliance. The analytes were isolated from plasma using liquid-liquid extraction and were separated on a Merck LiChroCART column with Superspher 60 RP Select B as the stationary phase. Gradient elution was performed using aqueous ammonium formate and acetonitrile. After screening and identification in the scan mode using the authors' LC/MS library, the analytes were quantified in the selected-ion monitoring mode. The quantification assay was fully validated. It was found to be selective proved to be linear from sub-therapeutic to over therapeutic concentrations for all analytes, except bromazepam. The corresponding reference levels the assay's accuracy and precision data for all studied substances are listed. The accuracy and precision data were within the required limits with the exception of those for bromazepam. The analytes were stable in frozen plasma for at least 1 month. The validated assay was successfully applied to several authentic plasma samples from patients treated or intoxicated with various benzodiazepines or with zaleplone, zolpidem or zopiclone. It has proven to be appropriate for the isolation, separation, screening, identification and quantification of the drugs mentioned above in plasma for clinical toxicology, e.g. in cases of poisoning, and forensic toxicology, e.g. in cases of driving under the influence of drugs. 相似文献