Selective non-radiative transitions at excited states of the self-trapped exciton in alkali halides

Generation of F-H pairs and σ-luminescence induced by excitation of the self-trapped excitons with polarized light causing the 1s→ 2p transitions has been measured. The results were analyzed based on the assumption that the non-radiative transitions that follow photoexcitation depend only on the state reached by the excitation, irrespective of the photon energy of the excitation. The absence of the dependence on exciting photon energy of the effective yield of removal from the triplet manifold after excitation to each substate obtained from the analysis proves that the above assumption is valid. The relative non-radiative transition probabilities between the 2p substates and from the 2p-substates to the lowest triplet state, the F-H pair, the σ-luminescent state and the ground state were obtained. It is shown that the de-excitation channels from each substate are substantially different from each other. The following transitions are found to have high probabilities: from the B_1g state to the F-H pairs in KCl and KBr, from theA_g state to the σ-luminescent state and the lowest triplet state in KBr and to the lowest triplet state in KCl and from the B_2g state to the B_1g state in KCl and KBr, where A_g, B_1g and B_2g denote the states with the electron excited to the σ_u orbital, the π_u orbital lying in the (100) plane in which the (halogen)₂^?-molecular ion is situated and the other π_u orbital, respectively. The mechanisms of these non-radiative transitions were discussed.     

Speculations on the absorption and emission properties of the F-centre in alkali halides

Summary A review of acquisitions and of unresolved problems concerning F-centres in alkali halides is presented. The main conclusions area) the temperature dependence of the bands is mainly due to the thermal expansion for the absorption process and to electron-phonon interaction for the emission process: for the latter half-width and Huang-Rhys factor values are related to the transverse optical frequency ones;b) the lifetime τ_R of the relaxed excited state is not intrinsic at low temperature because of the interaction between F-and α-centres always present in real samples;c) even though the absolute quantum yield decreases when F-centre concentration increased, the relative quantum yield η_r is unaffected by change on F-centre concentration, strongly evidencing a nonhomogenous distribution of F-centres in real samples;d) a temperature-dependent, fine structure in τ_R (an η_r) values is observed but only when temperature control of the samples is better than a few hundredth of a degree: this effect has been interpreted in terms of interactions which involve F-, α-and F′-centres. Work jointly supported by the Ministero della Pubblica Istruzione and by Consiglio Nazionale delle Ricerche, Gruppo Nazionale di Struttura della Materia.     

Unrestricted hartree-fock cluster analysis of F and F A centres in some alkali halides

The optical absorption energies and nearest-neighbour ground state hyperfine interaction constants are evaluated for F centres in lithium and potassium halides, and for FA(Li) centres in KC1 and KBr. For these defects, the electron-ion interaction includes self-consistent unrestricted Hartree-Fock treatment of nearest-neighbour ions, in terms of Gaussian-localized atomic orbital basis functions. The results, with the exception of FA-centre hyperfine constants, are qualitatively correct.     

The effect of plastic deformation on positron lifetime spectra in alkali halides

Positron lifetime spectra have been measured in plastically deformed KCl and NaCl single crystals. The experiments indicate that a third component of the order of 2 nsec is produced by the deformation, and its relative intensity (2–4%) is only weakly dependent on the degree of deformation.     

The Born repulsive parameters and dielectric behaviour of alkali halides

The dependence of the Born repulsive parameters of alkali halides on elastic and dielectric data has been discussed. The values of hardness parameter in alkali halides have been recalculated using the revised values of van der Waals energies. It is observed that the two sets of hardness parameter corresponding to elastic and dielectric data differ from each other but become compatible if an effective charge parameter for the ions is introduced. Its usefulness has been demonstrated by calculating the strain derivative of static dielectric constant of alkali halides.     

Anomalous decay and breather formation in doped alkali halides

Anomalous decay of doped alkali halides has been ascribed to breather formation in the immediate neighborhood of the impurity. New results support this connection. We report experimental data for NaBr and RbBr crystals showing anomalies in their slow emission decay. These data complete the earlier picture, confirming that the decay anomaly becomes bigger as the host-lattice-anion/cation mass ratio increases. We show the correlation between the decay anomaly and the breather formation as a function of this ratio. By simulating finite-temperature effects (which do not just involve white noise) in the lattice dynamics, we demonstrate that with increasing temperature the breather weakens, as is experimentally observed for the decay anomaly.     

The resonant secondary emission of the F center in alkali halides

The secondary radiation after resonant excitation of F center and its linear polarization P correlated to the polarization of resonant light have been measured for five alkali halides at low temperatures. In KC1, the spectrum of P over the whole Stokes region is divided into three successive regions, the depolarization range at the one-phonon Raman scattering, the near plateau range, and the depolarization range down to vanishing. The former two have common relevance to resonant energy and symmetries of coupled phonons. These relevances are interpreted adopting a configuration coordinate model for 2s- and 2p-like excited states.     

Self-, N2- and O2-broadening coefficients for the CO2 transitions near-IR measured by a diode laser photoacoustic spectrometer

Using a high-resolution tunable diode laser photoacoustic spectrometer, self-, N₂ and O₂ pressure broadening coefficients for the first 11 transitions of ¹²C¹⁶O₂ in the R branch of the (30012) ← (00001) overtone band at the 6348 cm⁻¹ have been revisited at room temperature (∼298 K). Air-broadening parameters have also been calculated from the N₂ and O₂ measurements. The dependence of the broadening on rotational quantum number m is discussed. The recorded lineshapes are fitted with standard Voigt line profiles in order to determine the collisional broadening coefficients of carbon dioxide transitions. The results are compared to our previous measurements and to the values reported in the HITRAN04 database and by other research group with a different spectroscopic technique.     

中国光声和光热技术研究进展回顾

光声光热技术引起国际科技界高度重视,已广泛应用于科学研究、高新科技和工业生产等领域。我国自上世纪70年代末、80年代初开展光声和光热学研究,至今已有许多科研单位从事包括光声光热谱、光声热波成像、光声光热技术、激光超声等方面以表征材料物理特性,并取得引人瞩目的成就。本文就我国在以上几个方面的主要技术工作进展给出简单的综述与回顾。     

Negative photoplastic effect due to the relaxed excited state of the F-center in alkali halides

Abstract

To make clear the mechanism of the photoplastic effect (PPE) in alkali halides containing F-centers, on the basis of the photochemical reaction of the F-center, temperature dependence of the PPE in KC1, and KBr and NaCl was studied from 95 K up to RT. The characteristic critical points θ _ts in colored KC1 and KBr were determined to be 110 and 190 K, respectively. Below θ _t the sign of the PPE in both crystals was negative, i.e., decrement of the flow stress during light illumination was observed. Moreover, the θ _ts were in good agreement with the temperature where the photoconductivities show remarkable increase in the course of the measurements. The negative PPE is explained in terms of the rotation of the principal strain axis of the relaxed state of the F-center having ?100? tetragonarity as to relax the stress around the edge dislocation coming closely.     

Ortho- to Para-Hydrogen Conversion and Molecular Diffusion in the High Pressure Compound Ar(H 2 ) 2

Ortho-para hydrogen conversion kinetics has been measured in the stoichiometric Ar(H 2 ) 2 compound, at pressures from 3 to 35 GPa, from the intensity of the rotational Raman transitions. The conversion rate increases with pressure by almost a factor 50 in the investigated pressure range. A comparison is made with pure hydrogen, where a similar increase is also observed. For long times and low ortho concentration, the conversion kinetic deviates from the law derived for uniform distribution of the ortho-hydrogen molecules in the crystal. The magnitude of this effect, due to the limited diffusion rate of the hydrogen molecules in the crystal, allows the measurement of the diffusion coefficient.     

The thermo-elastic instability model of melting of alkali halides in the Debye approximation

The Debye model of lattice vibrations of alkali halides is used to show that there is a temperature below the melting temperature where the vibrational pressure exceeds the electrostatic pressure. The onset temperature of this thermo-elastic instability scales as the melting temperature of NaCl, KCl, and KBr, suggesting its role in the melting of the alkali halides in agreement with a previous more rigorous model.     

Reflectance spectra and thermoluminescence of alkali halides coloured in an electrodeless discharge

Microcrystalline powders of NaCl, KCl and KBr are coloured in electrodeless discharge. Reflectance and TL studies of these coloured powders are reported. It is concluded that colouration of powders can be understood by considering them as an admixture of perfect and imperfect lattices, and differs from that of single crystals. It is suggested that some of the descrepancies reported on TL data may be due to such a difference. Further, it is shown that a better correlation can be had if TL data are presented along with the corresponding optical measurements. Adoption of such a procedure may help to remove the descrepancy in TL data.     

On Hurter-Driffield characteristics and optical storage in mixed crystals of alkali halides

Hurter-Driffield characteristic curves and the quality of stored and retrieved information in coloured mixed crystals of alkali halides are presented.     

High-pressure spectroscopic studies of free and self-trapped excitons in alkali halides at low temperatures

Abstract

A brief survey of our studies of free and self-trapped excitons (FE and STE) in alkali halide crystals under hydrostatic pressure up to 12.5 kbar at 4.2–140 K is presented. Main attention is paid to the following effects observed: (1) the strong coupling of three energy levels of FE in CsI revealing itself as an exciton analog of pressure-scanned Fermi resonance; (2) emergence of a new emission band of STE in CsI under pressure; (3) a large pressure shift of the thermal quenching curve for STE emission in NaCl.     

Heat and mass transport in the photoacoustic effect on liquids

The temperature oscillation accompanying the photoacoustic effect generates a periodic variation of the vapor pressure of a liquid. The propagation of the oscillating concentration of the vapor in the inert cell gas (air) is described by a mass diffusion wave on which a convective motion of the gas is superposed. The diffusion wave characterized by the diffusion coefficient of the cell gas alone can be measured by the Mirage effect, whereas a microphone detects the total mass flux including the convective flux, which increases with temperature. On approaching the boiling temperature, the convective flow will govern the oscillating transport of mass. The photoacoustic signal is determined directly from the flux of heat and mass at the boundary between liquid and gas using the Gauss' divergence theorem. We have found that the temperature behaviour of the amplitude and phase angle of the photoacoustic signal depends on the length of the gas column in the cell. The contribution of thermal expansion to the photoacoustic signal is considered using the composite piston model. The results of the calculations agree fairly well with the experimental data.     

The invar effect and phase transitions in Cs2ZnI4 crystals

An in situ x-ray diffraction study of Cs₂ZnI₄ crystals performed in the 4.2–300 K temperature range is reported. The lattice parameter measurements have revealed three anomalies corresponding to phase transitions. The thermal expansion coefficient along the c axis was found to vanish in the region of incommensurate and commensurate modulated phases, 120–96 K (the invar effect). A possible crystallographic model relating modulated atomic displacements to the invar effect is discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 137–142 (January 1999)     

The effect of size and composition on structural transitions in monometallic nanoparticles

Predicting the morphological stability of nanoparticles is an essential step towards the accurate modelling of their chemophysical properties. Here we investigate solid–solid transitions in monometallic clusters of 0.5–2.0 nm diameter at finite temperatures and we report the complex dependence of the rearrangement mechanism on the nanoparticle’s composition and size. The concerted Lipscomb’s Diamond-Square-Diamond mechanisms which connects the decahedral or the cuboctahedral to the icosahedral basins, take place only below a material dependent critical size above which surface diffusion prevails and leads to low-symmetry and defected shapes still belonging to the initial basin.     

The Dushinsky effect and sum rules for vibronic transitions in polyatomic molecules

A method is presented for analyzing, in terms of sum rules, the intensity distribution among the vibronic bands in electronic spectra of polyatomic molecules, taking into account the rotation of the excited-state normal coordinates relative to those of the ground state (the Dushinsky effect). In the harmonic oscillator approximation, a quantitative criterion for the occurrence of the Dushinsky effect is obtained. The existence of this effect leads to non-product formulas for probabilities of the joint excitation of different vibrational modes. Expressions are obtained for the mean number of quanta excited in a given mode, and for its standard deviation, as well as for the correlation coefficients. The proposed method does not require a complete vibrational analysis of the spectrum of interest. As an example, the calculation of the correlation coefficient for the 3700-Å band system of the absorption spectrum of SO₂ is given.