Spin-orbit coupling,spin-lattice relaxation,and spin-memory studies ofF-center-molecular-ion pairs in alkali halides

Summary The spin-orbit parameter Δ, spin-lattice relaxation timeT ₁, and spin-mixing parameter ɛ ofF _H(OH⁻) andF _H(CN⁻) centers in several alkali halides have been studied with magnetic circular dichroism at ∼2 K. A close comparison of the experimental results before and after optically induced association of theF center with the molecular ion has been made. In crystals of NaCl structure the negative spin-orbit parameter Δ changes little betweenF andF _H centers in the same host. For CsCl and CsBr two values of Δ have been derived forF _H(CN⁻) centers with axis parallel or perpendicular to the magnetic field. In all studied systems, the spin-lattice relaxation timeT ₁ is already shorter before aggregation compared toF formation. The spin-mixing parameter ɛ decreases slightly forF _H(OH⁻) compared toF centers, while it increases drastically forF _H(CN⁻) defects and reaches its maximum possible value ɛ=0.5 in cesium halides. First attempts to interpret these magneto-optical results will be presented. In honour of Prof. Fausto Fumi on the occasion of his retirement from teaching.     

On the ultrafast nonradiative relaxation of optically excited F2-centers

Single picosecond light pulses of a Nd-YAG excite-and-probe beam spectrometer are used for optical excitation of F₂-centers in LiF-OH. By measuring the rise of optical gain of these centers an upper limit of the configurational relaxation time could be estimated to be τ_nr < 10 ps. The emission cross section of F₂-centers at room temperature was found to be σ_e = (6 ± 2) x 10^-17cm².     

Relaxation dynamics of excited states of Tm3+ in SrGdGa3O7 crystals activated with Tm3+ and Tb3+

3 H₄ and ³F₄ states of Tm in SrGdGa₃O₇ single crystal was evaluated. Tm-Tb energy transfer reduces effectively the lifetime of terminal level in a potential ³H₄-³F₄ laser transition but gives rise to parasitic nonradiative relaxation of the initial ³H₄ level. SrGdGa₃O₇ crystal single doped with thulium possesses combination of properties advantageous for laser oscillations near 1.9 μm, namely high rate of cross relaxation process leading to population buildup on the initial ³F₄ level and relatively high crystal field splitting of the ground ³H₆ level. Received: 25 April 1996/Revised version: 10 October 1996     

A computational study of model hydrogen-, halogen-, beryllium- and magnesium-bonded complexes of aziridine derivatives

ABSTRACT

A computational study of the complexes F^?/H₂O…Z-aziridine, Z-aziridine…BeH₂/MgH₂ and F^?/H₂O…Z-aziridine…BeH₂ /MgH₂ (Z = Cl, H, Li) was undertaken in order to investigate the non-covalent interactions operative in the dimers and to assess their interplay in the trimer complexes. The halogen- and hydrogen-bonds between the O and Z atoms in F^?/H₂O…Z-aziridine are enhanced in the trimers by the Be(Mg) bond and vice versa, but the lithium bond is hardly affected. In the trimers containing F^?, the H bond is more dominant than the Be(Mg) bond, whereas the Be(Mg) bond is more dominant in the halogen- and lithium-bonded analogues. On the other hand, the Be(Mg) bond makes the major contribution to the energetic stability of all of the trimers containing H₂O.     

Excited state absorption and energy transfer losses in thulium doped fluoroindogallate glass

Thulium doped fluoroindogallate glass was characterized by means of excited state absorption experiment in the 0.95 to 1.55 μm spectral range. The three bands corresponding to the electronic transitions ³ F ₄→³ F ₂ (at 1.05 μm), ³ F ₄→³ F ₃ (at 1.125 μm), and ³ F ₄→³ H ₄ (at 1.45 μm) were observed. The energy transfer microscopic parameters for the reverse cross relaxation process ³ F ₄, ³ F ₄→³ H ₆, ³ H ₄ were calculated for different multipolar interaction mechanisms using the Kushida model, and it was verified that the probability of this process is 100 times lower than that of the direct ³ H ₄, ³ H ₆→³ F ₄, ³ F ₄ cross relaxation, responsible for the 1.8 μm emission pumping. PACS 78.20.-e; 78.55.Qr; 42.70.Hj; 42.55.Wd     

Ultrafast motion of liquids C2H4Cl2 and C2H4Br2 studied with a femtosecond laser

Transient optical Kerr effect of liquids C₂H₄Cl₂ and C₂H₄Br₂ is investigated, for the first time to our knowledge, with a femtosecond (fs) probe laser delayed with respect to a coherent fs pump laser. Coherent coupling and electronic Kerr signals are observed around zero delay when pump and probe overlap. Persisting after the pump-probe overlap are Kerr signals arising from the torsional and other intramolecular vibrations of the trans and gauche conformations; Kerr signals arising from the intermolecular motion are also observed. Vibrational quantum interference is only observed in liquid C₂H₄Br₂ and the related beats data are fitted with the torsional vibrations, 91 cm⁻¹ (gauche) and 132 cm⁻¹ (trans), and the CCBr angle-bending vibrations, 231 cm⁻¹ (gauche) and 190 cm⁻¹ (trans), with dephasing times, 0.45 ps, 0.45 ps, 2 ps, and 1.5 ps, respectively. These vibrational frequencies agree with those obtained in the frequency-domain. That no vibrational mode is observed for C₂H₄Cl₂ might be attributed to ineffective Raman-pumping. Kerr signals observed after the pump-probe overlap are Fourier transformed to give the spectra of the intermolecular motion and the vibrational spectrum, which agrees with the one observed in the infrared absorption and/or Raman scattering heretofore.     

Observation of defect clustering in Gd-doped calcium fluoride

Abstract

Solid solutions Ca_1-xGd_xF_2+x for 3 × 10^?7≤ x ≤10^?1 have been studied by electron paramagnetic resonance (EPR) and ionic thermal currents (ITC). The EPR experiments show the presence of two single-ion sites a cubic and a tetragonal Gd³⁺ center which co-exist with comparable abundances for intermediate impurity concentrations. The cubic center predominates at very low and high concentrations. Seven different relaxation processes have been identified from the ITC spectra and the variation of their intensity vs. x was measured. The absolute concentrations of the cubic and nn Gd³⁺ dipoles were calculated. The scavenging of interstitial fluorines by the neutral clusters explains both the abundance of cubic sites at high concentration and the variety of orientable clusters detected by ITC.     

The role of OH ions in the stabilization of F colour centres in LiF

Thermally Stimulated Depolarisation Current (TSDC) and optical methods are applied to a range of alkali-fluoride crystals in order to establish a model for the stable F ₂ ⁺ - like colour centres in LiF:OH^-. The experimental results for LiF:OH^- suggest that the OH^- defects are partially destroyed under ionising irradiation or during crystal growth. The low-temperature dielectric relaxation signals in LiF:OH^- and LiF:Mg²⁺,OH^- are attributed to highly interacting hydroxide ions and products of their destruction located in extended lattice defects. In LiF:OH^-, in contrast to other alkali halides, the results advocate for a defect-structure model, which considers a neutral defect (ND, probably O₂ or H₂) sited at the anion vacancy of the O^2--V _a ⁺ dipole and which possibly is the “nucleus” for the F ₂ ⁺ centre. The proposed F ₂ ⁺ (ND, O^-) model seems to better explain the dielectric results, compared to the older F ₂ ⁺ (O^2-) and F ₂ ⁺ (O^-) models. The estimate for the electric dipole moment derived from the experimental TSDC bands, gives a value for the F ₂ ⁺ - like centre in LiF:OH^- between those of the F ₂ ⁺ (O^-) and F ₂ ⁺ (O^2-) defects, in good agreement with the proposed F ₂ ⁺ (ND,O^-) model. The reduction of the activation energy barrier of the (re)orientation process of the Mg²⁺V _c ^- (OH^-) complexes in LiF:Mg²⁺,OH^-, and the low-temperature shift of their TSDC band, compared to the single Mg ₂ ⁺ V _c ^- peak in LiF:Mg²⁺, are tentatively ascribed to an increase in the crystal-lattice parameters owing to the presence of OH^- and/or products of its destruction. Received 31 August 2001 / Received in final form 30 March 2002 Published online 9 July 2002     

Vibrational properties of the F A (Li+) center in alkali halides

Abstract

The on- or off-axis behavior and the vibrational properties of the F _A (Li⁺) center are investigated in several alkali halides by means of polarized resonant Raman scattering. The observed Raman modes are interpreted and classified according to their nature and frequency. A comparison between on- and off-axis systems and between the vibrational modes of the isolated Li⁺ and the F _A (Li⁺) center reveals a displacement of the Li⁺ equilibrium position parallel to the F _A (Li⁺) defect axis and, due to the small impurity size, away from the adjacent F center.     

The lifetime of the 2pπu → 1sσg transition of the F2+ center in KCl

The lifetime of the 2pπ_u → 1sσ_g transition for the F₂⁺ center in KCl has been measured (15.8 ± 0.7 ns at 8 K) and found to be constant over the temperature range (8–90 K) investigated. No contradiction is found with the Aegerter and Lüty quantum yield data. A forecast for the lifetime of the 2pσ_u → 1sσ_g transition is also made, within the framework of the H₂⁺ model for the F₂⁺ center in alkali halides.     

Investigation of kerr-lens mode-locking of a flashlamp-pumped Nd:YAG laser

In this paper, we report that mode-locked operation is realized in a flashlamp-pumped Nd:YAG laser with a nearly critical stable resonator, using LiF:F₂⁻ color center crystal as a modulation device. A single pulse train with the energy of 25 mJ and the pulse duration of 82 ps is obtained. Both the theoretical and experimental results have shown that the mode-locked operation has resulted from kerr-lens effect formed in combination with self-focusing within Nd:YAG and an aperture at a specific point, but not directly from the saturable absorption of LiF:F₂⁻ crystal.     

Relaxation of the conductivity of CsI-Tl after excitation by subnanosecond electron pulses

The pulsed conductivity is investigated for a CsI-Tl crystal having a Tl⁺ concentration N=8×10¹⁷cm⁻³ and excited by an electron beam (0.2 MeV, 50 ps, 10²–10⁴ A/cm ²). It is shown that the amplitude of the conduction current pulse is almost an order of magnitude lower than for “pure” CsI crystals irradiated under like conditions. The conduction current relaxation time is preserved up to τ=100 ps in this case. Under the experimental conditions, therefore, the lifetime of electrons in the conduction band is controlled by trapping at Tl⁺ centers. The electron capture cross section at a Tl⁺ center is determined: σ=7×10⁻¹⁶ cm², which agrees in order of magnitude with estimates of the capture cross section for a neutral trapping center. Fiz. Tverd. Tela (St. Petersburg) 40, 66–67 (January 1998)     

Metastable F2 center states in LiF crystals

Using time-resolved pulsed absorption and luminescence spectroscopy we have studied the creation ofF ₂ centers during electron pulses of nanosecond duration in the temperature range 80 to 300 K. We show that the formation ofF ₂ centers in long-lived metastable states is thermally activated and competes withF ₂ center relaxation to the singlet state. It is shown that the S-T crossing in the set of states which describe theFC₂ center lies above the¹ _u level. We propose that when the crystal is excited with the lowest energy quanta which produce a photocurrent, the formation of tripletF ₂ centers takes place by localization of a conduction electron on anF ₂ ⁺ center.State Academy of Architecture and Construction, Tomsk. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 17–22, November, 1994.     

The temperature dependence of the hydroxyl deuterium quadrupole coupling parameter and the rotational correlation time of the OD internuclear vector in neat ethanol-d 1

The temperature dependence of the hydroxyl proton chemical shift and deuterium quadrupolar relaxation time of neat ethanol were measured over the temperature range 190–350 K. The proton isotropic chemical shift varies from 6.2 ppm at 190K to 4.7 ppm at 350 K. The deuterium NMR relaxation time in ethanol-d₁ varies from 6.2 ms to 309 ms over the same range. Ab initio calculations performed on various ethanol clusters ranging in size from monomer to hexamer show a linear correlation (R² = 0.99) between XD, the deuterium quadrupole coupling parameter, and δ_H, the isotropic proton chemical shift in ppm relative to TMS: XD(kHz) = 297.60 ? 15.28δ_H. The temperature dependence of XD ranges from 199.5kHz at 190K to 221.4 kHz at 350 K. Using the values for XD and the relaxation time data, the temperature dependence of the OD rotational correlation time was found to vary from 282 ps at 190 K to 4.5 ps near the boiling point (350 K). Using these correlation times and bulk viscosity data, the Gierer-Wirtz model predicts a supramolecular cluster volume of about 317 ų, the approximate volume of a cyclic pentamer cluter of ethanol molecules. The cluster volume was nearly constant from 340 K to about 290 K.     

Photon echoes and site-selective raman scattering of samarium-vacancy dipoles

Abstract

Electronic Raman scattering of Sm²⁺ in KCl is performed under resonant interconfigurational excitation around 500 nm. The position of the charge-compensating cation vacancy with respect to the substitutional Sm²⁺ ion is derived from both the Stark splitting of the J-levels and the polarization properties of the scattered light. The influence of the different site symmetries on the optical linewidth is investigated with photon echoes, stimulated from an accumulated grating, which is built up under intraconfigurational excitation between the ⁷ F ₀ and the ⁵ D ₁ terms of the 4f ⁶5 _s ²5 _p ⁶ ground state configuration. The echo decay time is about 10 ps and does not change sizably when tuning the excitation frequency over the inhomogeneous distribution. This shows that for zero-phonon line excitation, the Sm²⁺ sites are not very different. The temperature dependence of the echo is described by vertical relaxation to the bottleneck under multi-phonon emission.     

TmP5O14晶体的上转换发光的研究

报道室温下TmP₅O₁₄晶体在脉冲DCM染料激光激发下产生的紫外和深紫色上转换发光现象.测量发现在300—500nm波长范围内主要有两组上转换荧光,一是较强的¹D₂→³H₆,³F₄的360和450nm的双光子荧光,另一是¹I6→³F₄的347nm的三光于荧光,发现了由 关键词：     

Ion beam induced luminescence studies of LiAlO2 using negative ions

Lithium aluminate (LiAlO₂) is the candidate material for solid tritium breeder applied in the developing fusion reactors. The research of its defect behavior under ion irradiation was proceeded in the negative ions induced luminescence setup of the GIC4117 Tandem accelerator in Beijing Normal University. The ion beam induced luminescence (IBIL) measurement was performed by 20 keV H⁻ ions at room temperature. The luminescence spectra showed seven emission bands: the 4.55 eV may due to a self-trapped exciton (STE), the 4.06 eV and the 1.72 eV may due to impurity or intrinsic defect, the 3.54 eV due to F center, the 3.20 eV due to F⁺ center, the 2.93 eV due to F₂ center, the 2.30 eV due to F-center aggregates (F_n center), respectively. The intensity evolutions of each band with fluence were presented and the corresponding mechanisms were discussed.     

Photoexcitation of rare-gas neon and argon clusters doped with <Emphasis Type="Bold">H</Emphasis><Subscript><Emphasis Type="Bold">2</Emphasis></Subscript><Emphasis Type="Bold">O</Emphasis>

We have studied the fluorescence of electronically excited OH^*, H^* and H₂O^+* dissociation fragments after VUV excitation ( h ν≥11.6 eV) of rare-gas clusters (Rg = Ne, Ar) doped with H₂O molecules. In contrast to a free molecule, where Balmer H-series dominate the UV-visible spectra, only the OH ^* ( A ² Σ ⁺ ↦ X ² Π) emission band is observed in neon clusters. No emission of excited water ions has been observed. We find that while higher excitation energies (Ne vs. Ar) induce higher vibrational excitation of the OH^* ( A ) fragment, the rotational temperature is lower. This effect is attributed to the difference in the geometric position of the H₂O molecule on the surface or inside the Rg-cluster. The rotational relaxation in neon clusters is rapid while the vibrational relaxation is slow because of the coupling with the low energy matrix phonons. Received 7 March 2002 / Received in final form 27 May 2002 Published online 19 July 2002     

Longitudinal nuclear spin relaxation in solids in a triply rotating coordinate system: Selective observation of the multispin dipole contribution

The longitudinal nuclear spin relaxation in an effective magnetic field H _e3 acting in a triply rotating coordinate system is recorded. Rotating and doubly rotating coordinate systems are employed for strong suppression of the secular nuclear dipole interactions in the first two orders and for separation of higher-order interactions (four-and five-spin). Experiments on protons in polycrystalline benzene showed that the contribution of such multispin dipole interactions to this relaxation can be observed selectively as a pronounced local minimum in the temperature dependence of the relaxation time. This contribution correponds to ultraslow molecular motions with rates ≃ γH _e3≃2π(10¹−10³) s⁻¹ and can be employed to study such motions in detail, including for purposes of identification of the form of the motion. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 5, 335–340 (10 September 1996)     

Reductive Fluorescence Quenching of the Photoexcited Free Base <Emphasis Type="Italic">meso</Emphasis>-Tetrakis (Pentafluorophenyl) Porphyrin by Amines

Steady state and time resolved fluorescence quenching behaviors of meso-Tetrakis (pentafluorophenyl) porphyrin (H₂F₂₀TPP) in presence of different aliphatic and aromatic amines have been executed in homogeneous dichloromethane (DCM) solution. At room temperature in DCM, free base (H₂F₂₀TPP) shows fluorescence with two distinct peaks at 640 and 711 nm and natural lifetime τ _f = 9.8 ns which are very similar to that of meso-tetraphenyl porphyrin (TPP). Unlike TPP, addition of both aliphatic and aromatic amines to a solution containing H₂F₂₀TPP results in an efficient decrease in fluorescence intensity without altering the shape and peak position of fluorescence emission. Upon addition of amines there was no change in optical absorption spectra of H₂F₂₀TPP. The fluorescence quenching rate constants ranged from 1 × 10⁹ to 4 × 10⁹ s⁻¹, which are one order below to the diffusion control limit, and temperature dependent quenching rate constants yield the activation energies which are found to be order of 0.1 eV. Femto second transient absorption studies reveal the existence of amine cation radical and porphyrin anion radicals with very short decay time (15 ps). The fluorescence quenching reaction follows Stern–Volmer kinetics. Steady state and time-resolved data are interpreted within general kinetic scheme of Marcus semi-classical model which attributes bimolecular electron transfer process between amines and the lowest excited singlet state of H₂F₂₀TPP. Calculated internal reorganization energies are found to be in between 0.04 and 0.22 ev. Variation of electron transfer rate as function of free energy change (∆G⁰) points the ET reactions in the present systems are in Marcus normal region. This is the first example of reductive fluorescence quenching of free base neutral porphyrins in homogeneous organic solvent ever known.