929 resultados para Excited-state life time


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The multi-configuration Dirac Fock (MCDF) method is implemented to study doubly excited 2s2p P-1,3(1) resonances of the helium atom and the interference between photoionization and photo excitation autoionization processes. In order to reproduce the total photoionization sprectra, the excited energies from the ground 1s(2) S-1(0) state to the doubly excited 2s2p P-1,3(1) states and the relevant Auger decay rates and widths are calculated in detail. Further more, the interference profile determined by the so-called Fano parameters q and rho(2) is also reproduced. Good agreement is found between the present results and other available theoretical and experimental results. This indeed shows a promising way to investigate the Fano resonances in photoionization of atoms within the MCDF scheme, although there are some discrepancies in the present calculations of the 2s2p P-3(1) state.

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The beta-delayed neutron and gamma energy spectra taken from the decay of neutron-rich nucleus N-21 were measured by using the beta - gamma and beta - n coincidence detection method. Thirteen new neutron groups ranging from 0.28MeV to 4.98 MeV and with a total branching ratio of 88.7 +/- 4.2% were observed and presented. One gamma transition with an energy of 1222 keV emitted from the excited state of O-21, and four gamma transitions with energies of 1674, 2397, 2780, and 3175 keV emitted from the excited states of O-20 were identified in the 3 decay chain of N-21. The beta decay half-life for N-21 is determined to be 82.9 +/- 1.9 ms. The uncertainty of half-life is much smaller than the previous result.

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[Ru(bpy)2dppz]2+ electrochemiluminescence (ECL) was studied, and it was used to investigate DNA interaction and develop a label-free ATP aptasensor for the first time. ECL of [Ru(bpy)2dppz]2+ is negligible in aqueous solution, and increases approximately 1000 times when [Ru(bpy)2dppz]2+ intercalates into the nucleic acid structure. The ECL switch behavior of [Ru(bpy)2dppz]2+ is ascribed to the intercalation that shields the phenazine nitrogens from the solvent and results in a luminescent excited state. The ECL switch by DNA was applied to investigate the interaction of [Ru(bpy)2dppz]2+ with herring sperm DNA. The calculated equilibrium constant (K) is 1.35 x 10(6) M(-1), and the calculated binding-site size (s) is 0.88 base pair, which is consistent with the reported values.

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Four new iridium(III) complexes 1-4, with 1,3,4-oxadiazole derivative as cyclometalated ligand for the first time, have been synthesized and structurally characterized by NMR, EA, MS and X-ray diffraction analysis (except 1). The stronger ligand field strength of the dithiolate ancillary ligands results in higher oxidation potentials and lower HOMO energy levels of complexes than acetylacetone. The absorption spectra of these complexes display low-energy metal-to-ligand charge transfer transition ranging from 350 to 500 nm. Complexes with dithiolate ancillary ligand emit at maximum wavelengths of ca. 500 nm, blue shifting 17 and 11 nm with respect to their counterpart with acetylacetone ligand. The electrophosphorescent devices with 2-4 as phosphorescent dopant in emitting layer have been fabricated. All devices have a low turn-on voltage in the range of 4.5 and 4.9 V. A high-efficiency green emission with maximum luminous efficiency of 5.28 cd/A at current density of 1.37 mA/cm(2) and a maximum brightness of 2592 cd/m(2) at 15.2 V has been achieved in device using 2 as emitter.

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Two kinds of rare earth (RE) complexes were intercalated into zirconium bis(monohydrogenphosphate) (alpha -ZrP) by exchanging the RE complexes into the p-methyoxyaniline (PMA) preintercalated compound Zr(O3POH)(2). 2PMA (alpha -ZrP . 2PMA). Powder X-ray diffraction patterns reveal that Eu(DBM)(3)phen (DBM: dibenzoylmethane, phen: 1,10-phenanthroline) and Tb(AA)(3)phen (AA: acetylacetone) intercalated into alpha -ZrP . 2PMA. This was confirmed by the UV-visible spectra of both the RE complexes and the assemblies. At the same time, the assemblies have better luminescent properties, and the fluorescent lifetimes of RE3+ in the excited state in the assemblies are much longer than those in the complexes. The stabilities of the assemblies under UV radiation are much better than those of the RE complexes.

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Energy transfer processes between Eu2+ and Gd3+, Cr3+, Ce3+ ions in KMgF3, which are difficult to study spectroscopically, have been investigated by using the proposed four-level decay model of the P-6(7/2) excited state of the Eu2+ ion. Gd3+ and Ce3+ transfer its energy to the vibronic transition of the P-6(7/2) --> S-8(7/2) transition of Eu2+, whereas Cr3+ receive energy from Eu2+ via the d-d interaction. The energy transfer from the Eu2+ 4f(6)5d level to the Ce3+ 4f5d state is observed spectroscopically, and the energy transfer mechanism is discussed. (C) 2001 Elsevier Science B.V. All rights reserved.

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A method of fitting to Mossbauer spectrum of 151Eu has been proposed. The intensities and the positions of all the possible transitions between the sublevels of the ground state and those of the excited state of nucleus with spin I> 3/2 can be considered at one time in fitting to experimental Mossbauer spectra by this method. The method has been used to fit to the experimental Mossbauer spectra of europium orthophosphate crystal and of europium pentaphosphate crystal, and to derive Mossbauer parameters from...

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Ⅰ. INTRODUCTIONLaser-excited atomic fluorescence spectrometry in hollow cathode discharge(HCD) has been widely used in the research field of laser spectroscopy in recent years. Similar to traditional method, information obtained in the researches was direct line nonresonance fluorescence arising from the resonantly transitional upper level. Attention has not been sufficiently paid to the phenomenon of population change on the resonantly transitional lower level due to laser irradiation of plasma in HCD,...

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In this dissertation, we investigated two types of traveling ionospheric disturbances (TIDs)/gravity waves (GWs) triggered separately by auroral energy input during super geomagnetic storms and solar terminator (ST) under quiet geomagnetic conditions (kp<3+) using TEC measurements from the global network of GPS receivers. Research into the generation and propagation of TIDs/GWs during storms greatly enhance our understandings on the evolution processes of energy transportation from the high-latitude’s magnetosphere to the low-latitude ionosphere and the conjugated effect of TIDs propagation between the northern and southern hemispheres. Our results revealed that the conjugacy of propagation direction between the northern and southern hemispheres was subject to the influence of Coriolis force. We also figure out the evolution processes of ionospheric disturbances at the global scale. These are important topics that had not been well addressed previously. In addition, we also obtained thee wave structures of medium scale TIDs excited by the solar terminator (ST) moving over the northern America and physical mechanisms involved. Our observations confirm that the ST is a stable and repetitive source of ionospheric wave disturbances and the evidence of solar terminator generated disturbances has been demonstrated experimentally via the GPS TEC measurement. The main researches and results of this dissertation are as follows. First, the global traveling ionospheric disturbances (TIDs) during the drastic magnetic storms of October 29–31, 2003 were analyzed using the Global Position System (GPS) total electron content (TEC) data observed in the Asian-Australian, European and North American sectors. We collected the most comprehensive set of the TEC data from more than 900 GPS stations on the International GNSS Services (IGS) website and introduce here a strategy that combines polynomial fitting and multi-channel maximum entropy spectral analysis to obtain TID parameters. Moreover, in collaboration with my thesis advisor, I have developed an imaging technique of 2-dimensional map of TIDs structures to obtain spatial and temporal maps of large scale traveling ionospheric disturbances (LSTIDs). The clear structures of TEC perturbations map during the passage of TIDs were displayed. The results of our study are summarized as follows: (1) Large-scale TIDs (LSTIDs) and medium-scale TIDs (MSTIDs) were detected in all three sectors after the sudden commencement (SC) of the magnetic storm, and their features showed longitudinal and latitudinal dependences. The duration of TIDs was longer at higher latitudes than at middle latitudes, with a maximum of about 16 h. The TEC variation amplitude of LSTIDs was larger in the North American sector than in the two other sectors. At the lower latitudes, the ionospheric perturbations were more complicated, and their duration and amplitude were relatively longer and larger. (2) The periods and phase speeds of TIDs were different in these three sectors. In Europe, the TIDs propagated southward; in North America and Asia, the TIDs propagated southwestward; in the near-equator region, the disturbances propagated with the azimuth (the angle of the propagation direction of the LSTIDs measured clockwise from due north with 0°) of 210° showing the influence of Coriolis force; in the Southern Hemisphere, the LSTIDs propagated conjugatedly northwestward. Both the southwestward and northeastward propagating LSTIDs are found in the equatorial region. These results mean that the Coriolis effect cannot be ignored for the wave propagation of LSTIDs and that the propagation direction is correlated with the polar magnetic activity. (3) The day (day of year: 301) before the SC (sudden commencement) of magnetic storm, we observed a sudden TEC skip disturbances (±10 TECU). It should be a response for the high flux of proton during the solar flare event, but not the magnetic storms. Next, the most comprehensive and dense GPS network’s data from North-America region were used in this paper to analyze the medium scale traveling ionospheric disturbances (MSTIDs) which were generated by the moving solar terminator during the quiet days in 2005. We applied the multi-channel maximum entropy spectral analysis to calculated TID parameters, and found that the occurrence of ST-MSTIDs depends on the seasonal variations. The results of our study are summarized as follows: (1) MSTIDs stimulated by the moving ST (ST-MSTIDs) are detected at mid-latitudes after the passage of the solar terminator with the life time of 2~3 hours and the variation amplitude of 0.2~0.8 TECU. Spectral analysis indicated that the horizontal wavelength, average period, horizontal phase velocity of the MSTIDs are around 300±150 km,150±80 m/s and 25±15 min, respectively. In addition, ST-MSTIDs have wave fronts elongating the moving ST direction and almost parallel to ST. (2) The statistical results demonstrate that the dusk MSTIDs stimulated by ST is more obvious than the dawn MSTIDs in summer. On the contrary, the more-pronounced dawn MSTIDs occurs in winter. (3) Further analysis indicates that the seasonal variations of ST-MSTIDs occurrence frequency are most probably related to the seasonal differences of the variations of EUV flux in the ionosphere region and recombination process during sunrise and sunset period at mid-latitudes. Statistical study of occurrence characteristics of TIDs using the GPS network in North-American and European during solar maximum, In conclusion, statistical studies of the propagation characteristics of TIDs, which excited by the two common origins including geomagnetic storms and moving solar terminator, were involved with global GPS TEC databasein this thesis. We employed the multichannel maximum entropy spectral analysis method to diagnose the characteristics of propagation and evolvement of ionospheric disturbances, also, the characteristics of their regional distribution and climatological variations were revealed by the statistic analysis. The results of these studies can improve our knowledge about the energy transfer in the solar-terrestrial system and the coupling process between upper and lower atmosphere (thermosphere-ionosphere-mesosphere). On the other hand, our results of the investigation on TIDs generated by particular linear origin such as ST are important for developing ionospheric irregularity physics and modeling the transionosphere radio wave propagation. Besides, the GPS TEC representation of the ST-generated ionospheric structure suggests a better possibility for investigating this phenomenon. Subsequently, there are scientific meaning of the result of this dissertation to deeply discuss the energy transfer and coupling in the ionosphere, as well as realistic value to space weather forecast in the ionosphere region.

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The photodissociation of C6H5Br at 266 nm has been investigated on the universal crossed molecular beam machine, and time-of-flight spectra as well as the angular distribution of Br atom have been measured. Photofragment translational energy distribution P(E-t) reveals that about 47% of the available energy is partitioned into translational energy. The anisotropy parameter beta at this wavelength is -0.7+/-0.2. From P(E-t) and beta, we deduce that C6H5Br photodissociation is a fast process and the transition dipole moment is almost perpendicular to the C-Br bond. Ab initio calculations have been performed, and the calculated results show that the geometry of the first excited state of bromobenzene has changed apparently compared with that of the ground state. Two kinds of possible fast dissociation mechanism have also been proposed. (C) 1999 American Institute of Physics. [S0021-9606(99)01206-4].

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The bifunctional complex [Ru(TAP)(2)POQ-Nmet](2+), 1, formed with a [Ru(TAP)(2)Phen](2+) metallic unit linked to a quinoline moiety, and [Ru(TAP)(2)Phen](2+), 2, as reference, have been tested as photoprobes of DNA. Interestingly, 1 exhibits an emission enhancement of a factor of 16-17 upon binding to calf thymus DNA. Moreover, this emission is modulated by the nucleic base content of the polynucleotide. It varies by almost an order of magnitude from a polynucleotide containing 100% of G-C to a guanine-free nucleic acid where the excited-state lifetime reaches about 2 micros. The origins of these interesting properties are analyzed by comparing 1 with reference 2 in the presence of different polynucleotides.

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Use of phase transfer catalysts such as 18-crown-6 enables ionic, linear conjugated poly[2,6-{1,5-bis(3-propoxysulfonicacidsodiumsalt)}naphthylene]ethynylene (PNES) to efficiently disperse single-walled carbon nanotubes (SWNTs) in multiple organic solvents under standard ultrasonication methods. Steady-state electronic absorption spectroscopy, atomic force microscopy (AFM), and transmission electron microscopy (TEM) reveal that these SWNT suspensions are composed almost exclusively of individualized tubes. High-resolution TEM and AFM data show that the interaction of PNES with SWNTs in both protic and aprotic organic solvents provides a self-assembled superstructure in which a PNES monolayer helically wraps the nanotube surface with periodic and constant morphology (observed helical pitch length = 10 ± 2 nm); time-dependent examination of these suspensions indicates that these structures persist in solution over periods that span at least several months. Pump-probe transient absorption spectroscopy reveals that the excited state lifetimes and exciton binding energies of these well-defined nanotube-semiconducting polymer hybrid structures remain unchanged relative to analogous benchmark data acquired previously for standard sodium dodecylsulfate (SDS)-SWNT suspensions, regardless of solvent. These results demonstrate that the use of phase transfer catalysts with ionic semiconducting polymers that helically wrap SWNTs provide well-defined structures that solubulize SWNTs in a wide range of organic solvents while preserving critical nanotube semiconducting and conducting properties.

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This paper describes how modeling technology has been used in providing fatigue life time data of two flip-chip models. Full-scale three-dimensional modeling of flip-chips under cyclic thermal loading has been combined with solder joint stand-off height prediction to analyze the stress and strain conditions in the two models. The Coffin-Manson empirical relationship is employed to predict the fatigue life times of the solder interconnects. In order to help designers in selecting the underfill material and the printed circuit board, the Young's modulus and the coefficient of thermal expansion of the underfill, as well as the thickness of the printed circuit boards are treated as variable parameters. Fatigue life times are therefore calculated over a range of these material and geometry parameters. In this paper we will also describe how the use of micro-via technology may affect fatigue life

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Flexible luminescent polymer films were obtained by doping europium(III) complexes in blends of poly(methyl methacrylate) (PMMA) and the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(6)mim][Tf2N]. Different europium(III) complexes have been incorporated in the polymer/ionic liquid matrix: [C(6)mim][Eu(nta)(4)], [C(6)mim][Eu(tta)(4)], [Eu(tta)(3)(phen)] and [choline](3)[Eu(dpa)(3)], where nta is 2-naphthoyltrifluoroacetonate, tta is 2-thenoyltrifluoroacetonate, phen is 1,10-phenanthroline, dpa is 2,6-pyridinedicarboxylate ( dipicolinate) and choline is the 2-hydroxyethyltrimethyl ammonium cation. Bright red photoluminescence was observed for all the films upon irradiation with ultraviolet radiation. The luminescent films have been investigated by high-resolution steady-state luminescence spectroscopy and by time-resolved measurements. The polymer films doped with beta-diketonate complexes are characterized by a very intense D-5(0) -> F-7(2) transition ( up to 15 times more intense than the D-5(0) -> F-7(1)) transition, whereas a marked feature of the PMMA films doped with [choline](3)[Eu(dpa)(3)] is the long lifetime of the D-5(0) excited state (1.8 ms).

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Resonance Raman (RR) spectroscopy has been used to probe the interaction between dipyridophenazine (dppz) complexes of ruthenium(II), [Ru(L)(2)(dppz)](2+) (L = 1,10-phenanthroline (1) and 2,2-bipyridyl (2)), and calf-thymus DNA. Ground electronic state RR spectra at selected probe wavelengths reveal enhancement patterns which reflect perturbation of the dppz-centered electronic transitions in the UV-vis spectra in the presence of DNA. Comparison of the RR spectra recorded of the short-lived MLCT excited states of both complexes in aqueous solution with those of the longer-lived states of the complexes in the DNA environment reveals changes to excited state modes, suggesting perturbation of electronic transitions of the dppz ligand in the excited state as a result of intercalation. The most prominent feature, at 1526 cm(-1), appears in the spectra of both 1 and 2 and is a convenient marker band for intercalation. For 1, the excited state studies have been extended to the A and A enantiomers. The marker band appears at the same frequency for both but with different relative intensities. This is interpreted as reflecting the distinctive response of the enantiomers to the chiral environment of the DNA binding sites. The results, together with some analogous data for other potentially intercalating complexes, are considered in relation to the more general application of time-resolved RR spectroscopy for investigation of intercalative interactions of photoexcited metal complexes with DNA.