首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Within the framework of the method of a density matrix, differential equations are obtained that describe the evolution of the modes of magnetization <Î+>, <Î+ z >, and <Î+ z 2> for a spin system containing a nucleus with a 1/2 spin connected scalarly with the quadruple nucleus of the spin S = 1 in the presence of crosscorrelation between the dipole ISinteractions, anisotropy of the chemical shift of the I and S nuclei, and quadruple interaction of the S nucleus. The equations are used for analysis of the evolution of the intensities of each line in the triplet of the Raman spectrum of the 1/2 spin. Expressions for the times of crossrelaxation and the times of transverse relaxation of each of the lines of the triplet are obtained.  相似文献   

2.
Resonance Raman spectra (RRS) of Co(II) and Co(III)5,10,15,20tetrakis(4Nmethylpyridinium)porphyrin ((CoII(TmpyP4), and CoIII(TMPyP4)) in aqueous solutions at different pH as well as in organic solvents (methanol, ethanol, DMSO, DMF) are obtained. The increased sensitivity of the oscillation frequencies 2, 4, 8, and 6 — the markers of the oxidation state of a metal — to the nature of an axial ligand has been revealed. For CoIII(TmpyP4), the shifts of the indicated frequencies in extracoordination have turned out to be twofold larger than those for CoII(TmpyP4). The spectral effects observed are related to different electron influence of the extraligands on the system of the porphyrin ring. In the case of Co(III)porphyrin, interaction of the d orbitals of the metal and the e g *orbitals of the macrocycle is more efficient since its ionic radius is smaller than for the Co(II)complex. For CoIII(TmpyP4), a linear correlation between the oscillation frequencies 2, 4, 8, and 6 and the experimental Gutmann parameters characterizing the electronacceptor properties of solvents is found.  相似文献   

3.
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 0T 1. The transitions up to S 0S 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 0S 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 0T 1 band is observed.  相似文献   

4.
Using the DFT/B3LYP method with the base set 631G**, we carried out calculation of the frequencies of the normal vibrations of porphin and of its five isotopic types. Scaling of force constants for outofplane vibrations has been performed in independent natural coordinates. The symmetry coordinates are introduced and a force field for outof plane vibrations of a porphin molecule in independent coordinates of symmetry is obtained. A new correlation of the frequencies of vibrations in the type of the symmetry B 1u for the isotopic type of the d 2 porphin molecule is suggested on the basis of discrete analysis of the distribution of a potential energy.  相似文献   

5.
Based on a solution of the stationary modified Bloch equations, an investigation is made of the influence of the effect of internal optical bistability (IOB) on the behavior of the refractive index of a dense resonance medium as a function of the constant b of closerange dipoledipole interactions, frequency detuning, and the intensity of optical radiation. The conditions of existence of the IOB effect of the system dense resonance medium + optical radiation are found and the dynamics of the loop width of the hysteresis dependence of the population difference of the resonance levels of the medium on the characteristics of the system is traced. The domains of the parameters are determined in which the effects of selffocusing and selfdefocusing of the radiation propagating in a dense resonance medium can take place.  相似文献   

6.
We have analyzed the energetics of decay of the X minus trion (exciton + electron) on the assumption that the exciton and trion are independent excitations of a single twodimensional semiconducting quantum well. For the first time, it has been shown that in filling a well with electrons from a selective donordoped matrix, the binding energy of the trion (of the electron with the exciton) increases linearly with a shift of the Fermi level into the depth of the c band. This agrees with the wellknown experimental data on the lowtemperature radiative decay (photoluminescence) of trions in the heterostructures ZnSe/Zn0.89Mg0.11S0.18Se0.82 and CdTe/Cd0.7Mg0.3Te.  相似文献   

7.
For the first time, the antiStokes luminescence in colloidal solutions of CdTe nanocrystals on excitation below the absorption edge has been discovered. The maximum spectral shift to the shortwave region relative to the excitation energy E con max = 319 meV is obtained for meansized nanocrystals (2.5 nm). The conversion efficiency of the absorbed radiant energy is 1.3·10–2%. The rise in the antiStokes photoluminescence intensity with increasing temperature and the linear dependence on the exciting radiation intensity have been established. It is shown that the effect observed cannot be caused by twophoton excitation or by Auger recombination. It is assumed that the basic mechanism of the luminescence observed is the radiative recombination through the energy levels of the states attributable to the disturbance of the crystal structure in the nanocrystals.  相似文献   

8.
Pentamers of two types have been obtained in aqueous solutions containing mixtures of two tetrapyrrole compounds, in whose molecules there are positively or negatively charged peripheral groups. The pentamers of one type include one molecule of mesotetra(4Nmethylpyridyl) porphin (TMPP) and four molecules of the complex of mesomono(nsulfophenyl)etioporphyrin II with palladium (PdSPhEP), and the pentamers of the other type include one molecule of sulfonated phthalocyanine (PCS) and four molecules of TMPP. The absorption bands of the pentamers are broadened and shifted toward longer wavelengths in comparison with the bands obtained as a result of the addition of the spectra of the monomers. It seems that the changes in the absorption spectra are first of all due to the change in the interaction of the molecules of the pigments with the molecules of the surrounding in formation of associates and due to the influence of the resonance dipoledipole interaction between the molecules in the associates. The influence of the intermolecular photoinduced charge transfer is also possible (it is most probable for the associates with PCS). We have revealed an effective quenching of the fluorescence of PCS and TMPP solutions upon heteroassociation.  相似文献   

9.
In the present article, undoped and Codoped Mtype Srhexaferrites have been prepared at low temperatures down to 980 C for the first time by the usual ceramic procedure and sintering technique. On these materials, a CoK Xray diffraction analysis and the room temperature 57Fe Mössbauer spectroscopy (MES) were carefully performed. The results obtained are described and interpreted. The mechanism of Co substitution partially in place of iron and the site of its occupancy were proposed and established.  相似文献   

10.
Spectral manifestations of protolytic forms of 1aza2methyl6aminopyrene in ethanol and aqueous solutions are investigated. The ionization constants of the protolytic forms are determined. The generation properties and photostability of a neutral molecule and a cation in excitation by an excimer XeCl laser are studied.  相似文献   

11.
Four new Hofmanntype complexes, M(DMTF)2Ni(CN)4, (where DMTF is dimethylthioformamide, M=Mn, Cd, Co, or Ni) were synthesized and their structure was determined by an elemental analysis and infrared spectroscopy. The IR spectra of DMTF and its nickel tetracyanine complexes with Mn(II), Cd(II), Co(II), and Ni(II) have been investigated within the range 4000–400 cm–1. The frequency shifts in the metal complexes agree with the assignment of the CS and CN frequencies. The complexes consist of infinite planar polymer layers of |MNi(CN)4|. Ndimethylthioformamide is coordinated to this layer from above and below; it is a monodentate ligand and is Sbonded through the metal atom in these complexes.  相似文献   

12.
A simple technique using a novel twofrequency Bragg grating based Brillouin fiber laser to downconvert high frequency microwave photonic signals is presented. The mechanism of the Brillouin fiber laser and the principle of this technique for microwave photonic signal downconversion are analyzed. The 12GHz microwave photonic signals are experimentally downconverted to 1.13GHz IF signal with the technique.  相似文献   

13.
A procedure of xray spectral fluorescence analysis of the elemental composition of As x S100–x chalcogenide powder samples is developed and its metrological characteristics are established. In determining the content of the components in an As50S50 sample, the relative standard deviation was 0.0030 for As and 0.0035 for S. The results of the xray spectral fluorescence analysis are in good agreement with the data of a gravimetric method.  相似文献   

14.
We investigated fluorescence and fluorescence excitation spectra of five substituted diphenylpolyenes with the number of double bonds in the chain n = 2 or n = 3 and substituents NO2, N(CH3)2, and NH2 in different media (toluene and noctane) at low (77 and 4.2 K) temperatures. The duration of fluorescence () and the quantum yield of fluorescence () of the four compounds investigated were measured at room temperature. The influence of the electron donoracceptor interaction in one of the compounds on its spectralluminescent properties has been analyzed.  相似文献   

15.
Using methods of emission spectroscopy, we have determined the gaskinetic temperature fields of planar highfrequency capacitive discharge plasma in N2/CO2/He gas mixtures depending on the excitation frequency, discharge current, pressure, and chemical composition of the mixture. It is shown that the dominant contribution to the neutral component heating in the center of the discharge chamber is made by the processes of VT relaxation of vibrationally excited molecules N2(X 1, V) and CO2(X 1, V), whereas in the zones near the electrodes an important role in the heating is played, along with the VT relaxation of the N2(X 1, V) and CO2(X 1, V) molecules, by the processes of deactivation of the metastable states A 3 of the N2 molecule.  相似文献   

16.
It is shown that the molecules of the free base of porphin (H2P) incorporated into an inorganic tetraethoxysilane (TEOS) gel matrix produce a dication form H4P2+. A finestructure spectrum of the fluorescence of H4P2+ is obtained at 4.2 K on selective photoexcitation. A conclusion on the manifestation of the outofplane vibrations of the porphyrin macrocycle in the lowfrequency region of the vibronic spectrum of porphin dication is drawn and the assignments of the corresponding frequencies to the vibrations of a certain form are suggested.  相似文献   

17.
Using the CNDO/S method, we have performed quantumchemical calculations of the ground and excited electronic states of porphin molecules (symmetry D 2h ) and a number of porphin isomers: porphycene (C2h ), hemiporphycene, corphycene (C2v ), isoporphycene, and three nonsynthesized structural isomers of the porphin skeleton by its bridge groups —(CH) meso —. The results of the calculations are compared with the corresponding data for the freebase porphin molecule (H2P). Near the boundary between the occupied and vacant orbitals the isomers form rows of singleelectron levels with similar energy characteristics. For the MOs of these isomers, the H2P MOs closest in distribution on the comparable atomic centers are given. The weak (Q) and strong (B) transitions in the visible and near UV regions point to the porphyrin type of spectra of all the isomers. The calculation data on the excited electronic states of N, g, and ntype H2P near and above the B states are given; the presence of such states in other isomers is shown. The calculation does not point to a difference in the position of the first singlet transitions in the first five isomers. The calculation data on the lower singlettriplet transitions are also reported.  相似文献   

18.
Using the methods of atomicforce microscopy, xray diffractometry, and spectrophotometry, we have studied the morphological, structural, and optical characteristics of GRSactive substrates based on original and annealed silver films. We show that the backing temperature during deposition is the factor which exerts the most substantial effect on the morphological and optical properties of silver films and also on their stability with time. The coefficients of the correlation of the deposition rate with the characteristics of the optical density spectra of silver films are calculated. It is found that hightemperature (350°C) annealing of a silver film leads to the selforganization of its surface into a quasiperiodic structure with semiellipsoidal islets. The contribution of the processes of excitation of plasma resonances to the formation of the optical density spectra is discussed. It is shown that as a result of thermal modification the concentration of the crystalline phase of silver in a silver film increases 2–3 times and also the dispersion of the orientation of crystallites decreases.  相似文献   

19.
IR integrated photonic amplifiers at 1.55m operation will have good foreground in optical phasedarray radars for splitters and signal processing. The saturation gain characteristics of IR integrated photonic waveguide amplifiers (taken Er3+Yb3+ co-doped phosphate glass waveguide amplifiers as an example) are studied theoretically. For the homemade laser glass materials the calculated saturation intensities are 2.22kw /cm2 for signal and 10.15kw/cm2 for pump. The effects of absorption saturation of signal and pump lights on the gain of amplifiers are discussed.  相似文献   

20.
In the electron energy loss spectra (EELS) of the organic europium complexes Eu3+ (BTFA)3TPPO and Eu3+(BrBTFA)3TPPO in a gas phase obtained on excitation by monokinetic beams of electrons of different energies in the range 12–50 eV, we have identified the bands associated with the electron transitions S 0S 1, S 0S 2, and S 0S 3. The connection of these transitions with the structural groups of the complexes is established. The addition of the bromine atom to the phenyl ring of diketonate leads to the rise in the relative intensity of the S 0S 2 band. The singlettriplet transitions manifest themselves in the region 2.5–3.2 eV and contribute to the S 0S 2 band of the electron energy loss spectra.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号