Er3+离子掺杂钡镓锗玻璃上转换发光机理研究

研究了Er³⁺离子掺杂钡镓锗玻璃的吸收光谱、拉曼光谱和上转换光谱.分析了Er³⁺离子在钡镓锗玻璃中的上转换发光机理.结果表明：玻璃的最大声子能量为828cm^-1，紫外截止波长为275nm.采用800nm和980nmLD激发玻璃样品，在室温下观察到强烈的上转换绿光和红光发射.随着Er³⁺离子浓度的增加，绿光发光强度先增加后减小，而红光发光强度呈单调递增趋势.能量分析表明：800nmLD激发产生的绿光主要源于Er³⁺离子4I_13/2能级的激发态吸收过程；红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程.980nmLD激发产生的绿光主要源于Er³⁺离子4I_11/2能级之间的能量转移过程；而红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程和4I_13/2能级的激发态吸收过程.通过量子效率分析，发现采用800nmLD激发Er³⁺离子掺杂浓度为1mol% 的样品时，上转换绿光发光效率最高. 关键词： 上转换发光机理 3+离子掺杂')" href="#">Er³⁺离子掺杂 钡镓锗玻璃     

Influence of short-and long-range interaction forces on the efficiency of collisional vibrational energy transfer in the vibrational quasi-continuum

Based on measurements of the time-resolved delayed fluorescence, the influence of universal interactions on the collisional vibrational energy transfer is studied in mixtures of vibrationally excited polyatomic molecules (acetophenone, benzophenone, and anthraquinone) with inert bath gases (Ar, C₂H₄, SF₆, CCl₄, and C₅H₁₂). From the dependences of the decay rates of delayed fluorescence on bath gas pressure, the efficiencies of the establishment of vibrational (V-V relaxation) and thermal (V-T relaxation) equilibrium after excitation of molecules into the vibrational quasi-continuum of a triplet state are estimated. The main emphasis is on studying the dependences of the efficiency of collisional vibrational energy transfer on temperature and the molecular characteristics of collision partners. It is found that the efficiency increases with the complication of the structure of bath gases for the V-V process and decreases upon the increasing of their mass for the V-T process. For the temperature range 273–553 K, the negative temperature dependence of the V-V transfer probability and the positive (Landau-Teller) dependence of the V-T transfer probability were obtained. It is concluded that the above regularities reflect the dominant role of long-range attractive forces in initiating the quasi-resonant V-V transfer and of short-range repulsive forces in the V-T transfer of vibrational energy.     

Vibrational excitation of a molecule by a resonance current

Correct expressions are obtained for calculating a tunnel-resonance current through molecules. The participation of molecular vibrations in the resonance charge transfer through a molecule and vibrational excitation of the molecule are determined by the reorganization energy E _r of the vibrational system depending on the displacement of the equilibrium position of vibrational modes in passing from the neutral molecule to the resonance state of a molecular ion. The mean excitation energy of the molecule during the propagation of an elementary charge changes from E _r at the voltage across electrodes close to the threshold up to 2E _r at voltages considerably exceeding the threshold voltage. An expression is obtained for the stationary vibrational temperature of the molecule, which is proportional to the resonance current.     

Radiative lifetimes and collisional quenching cross sections of selectively excited vibrational states of the B 2p1Σu+ state of H2

Radiative lifetimes between 0.54 ns and 0.69 ns have been measured for the vibrational levels υ′ = 0...4 of the B 2p¹Σ_u⁺ state of H₂ after selective excitation by synchroton radiation. Quenching by collisions with H₂ ground state molecules has been observed with cross sections of 5 × 10^-15 cm².     

Microwave spectroscopy of OCS in highly excited vibrational states through energy transfer from N2

The efficient vibrational energy transfer between the first excited vibrational state of N₂ and the asymmetric stretching vibrational state of OCS has allowed the observation of many pure rotational lines in different vibrational states of OCS up to 4101 cm^?1: (00⁰1), (01¹1), (02^l1), (10⁰1), (00⁰2), (21¹0), (03^l0), (04^l0), and (05^l0). Accurate values of some rotational, centrifugal distortion and l-doubling constants are determined.     

The rotation-vibration spectrum and double-minimum ν12 potential function of propadienone: A semirigid bender analysis

Propadienone is an interconverting molecule having a pair of equivalent symmetry related conformers separated by an energy barrier rising well above the vibrational ground state. Microwave spectra of molecules in excited states of the large-amplitude in-plane bending mode ν₁₂, including intersystem lines, have been successfully represented using the semirigid bender model. The model reveals a double-minimum bending potential with a barrier rising 359 cm⁻¹ above the minima at C₁C₂C₃ = 142°. In the ground state the interconversion frequency is 3.7 GHz and the ν₁₂ fundamental frequency is predicted to be 160 cm⁻¹. Analysis of other vibrational satellites involving the lowest-frequency out-of-plane mode ν₈ indicates a vibrational frequency of 240 cm⁻¹. The inplane vibrational satellite and also the ground state substitution spectra are quite accurately reproduced by the model. Our generalized semirigid bender method offers a variety of approaches to fitting molecular parameters to the experimental data.     

Energy transfer processes in linear triatomic molecule-solid surface collisions

The semiclassical stochastic trajectory method is extended to the study of rotational and vibrational transitions for linear triatomic molecules colliding with non-rigid solid surfaces. Rotational and vibrational motion are treated by quantum mechanics, translational motion by classical mechanics, and surface atom motion by the classical generalized Langevin equation. Self-consistent coupling of all motions is enforced via Ehrenfest's theorem. Calculations of the kinetic energy and gas temperature dependence of trapping probabilities, vibrational relaxation probabilities and final vibrational state distributions are presented for the CO₂-Ag(111) system at surface temperatures of 0 and 600 K. The trapping probabilities are greatly enhanced by the rotational motion and also vary to some degree with the initial vibrational state of the CO₂. Total vibrationally inelastic probabilities are on the order of 10⁻² for a single collision event with an initial state (00°1). For the initial state (01¹0) these are much larger, ~ 10⁻¹, due to the nature of bending mode motion. In conjunction with the large trapping probabilities, the mechanism of vibration to vibration, rotation, translation, phonon energy transfer can provide vibration relaxation probabilities in the range of those measured experimentally. A pseudo-selection rule for conservation of vibrational angular momentum is found.     

Yrast levels of 220Ra populated in the 208Pb(14C, 2n) reaction

Yrast states in the nucleus ²²⁰Ra were studied by means of the ²⁰⁸Pb(¹⁴C, 2n) reaction at 61 and 64 MeV. A staggering sequence of levels of positive and negative parity has been observed up to spin and parity I^π = 16⁺ (18 ⁺) and from I^π = 5^? to I^π = 17^?, respectively. These states are connected by strong E1 transitions competing with the stretched E2 transitions, the $\text{B(}\text{E}\text{1)}\text{B(}\text{E}\text{2)}$ ratio being ~ 10 ^?6 fm^?2. The ratio of the excitation energy of the 4⁺ state to that of the 2⁺ state is close to the vibrational limit. The moment of inertia associated with the negative-parity yrast states is slightly increasing with the rotational frequency ω. It is considerably higher than that of the positive-parity states at lower spins, the difference decreasing monotonically with increasing ω. The data are discussed with reference to the octupole vibrational picture as well as to the results of recent models predicting reflection-asymmetric shapes in the Ra-Th region.     

Millimeter- and submillimeter-wave length spectrum of the partially deuterated ammonias; A study of inversion,centrifugal distortion,and rotation-inversion interactions

Eighty-two new rotation-inversion transitions of the light asymmetric rotors NH₂D and ND₂H have been measured in the 80–600 GHz region by means of high resolution microwave techniques. Included among these transitions are several submillimeter R-branch transitions which make possible a calculation of both the rotational and distortion parameters which characterize the molecule. An accurate inversion Hamiltonian is developed and used as a preliminary step to a rotation-distortion treatment of the molecule. The spectrum of ND₂H reveals the existence of a rotation-vibration interaction which significantly alters the energy of a number of ground vibrational state levels. The results of an analysis technique which incorporates the effects of this perturbation as well as the inversion effects are presented. This procedure makes possible the analysis of all observed transitions to within experimental uncertainties as well as the accurate prediction of unobserved transitions. The rotational constants which result from this work are (MHz): For NH₂D, O⁺ vibrational state,a= 290 286.53 ± 0.21,B= 192 240.15 ± 0.42,C= 140 602.50 ± 0.42; for NH₂D, O^? vibrational state,a= 290 192.14 ± 0.21,B= 192 176.27 ± 0.42,C= 140 625.64 ± 0.42; for ND₂H, O⁺ vibrational state,a= 223 222.92 ± 0.18,B= 160 433.96 ± 0.17,C= 112 305.40 ± 0.17; for ND₂H, O^? vibrational state,a= 223 147.21 ± 0.14,B= 160 423.37 ± 0.13,C= 112 313.72 ± 0.13.     

Ab initio potential energy curves and vibrational levels for the c, l, and i states of the hydrogen molecule

Potential energy curves for the hydrogen molecule in the c³Π_u, I¹Π_g, and i³Π_g state have been calculated in the Born-Oppenheimer approximation. Highly flexible wavefunctions have been used, and for each state the calculations have been carried out for 40 different internuclear distances in the region 1 ≤ R ≤ 12 a.u. For the Π_g states the wavefunctions are known to change their character around R = 5 a.u. The effect of this change on various components of the energy has been analyzed. The vibrational Schrödinger equation for all states has been solved for H₂, HD, and D₂. For H₂ the resulting energies are compared with the experimental values and it is shown that the adiabatic effects are likely to be responsible for the existing discrepancy between the theoretical and experimental values.     

Determination of relaxation times of ground electronic state vibrational levels of mixed molecular crystals

The stimulated emission spectra of mixed molecular crystals were investigated with the Nd glass lasser third harmonic excitation at 4.2 K. Napthalene crystals doped with β-naphthyl-n-biphenylyl ethylene and dibenzyl doped with naphthacene in various concentrations were studied. Relaxation times of the ground state vibrational levels in mixed molecules were obtained by use of the dependence of stimulated emission intensity upon excitation energy for naphthacene in dibenzyl τ₁ of the vibrational level at 317 cm^-1 was ～ 3 × 10^-9 s; for β-naphthyl-n-biphenylyl ethylene in naphthalene τ₁ of the 1629 cm^-1 vibrational level was ～ 10^-10 s.     

Optical losses in YVO4: RE (RE = Nd3+, Er3+, Tm3+) laser crystals

The relevance of processes contributing to depletion of pump and upper laser levels has been assessed based on experimental data obtained during measurement of excited state absorption, steady state emission and dynamics of excited states as a function of excitation power and activator concentration. It has been concluded that the excited state absorption in YVO₄: Nd and YVO₄: Er is not significant except for that from the ⁴ I _11/2 level of Er³⁺. In these systems, the interionic processes are dominant. In particular, the reported decrease of the YVO₄: Er laser slope efficiency when the Er³⁺ concentration increased from 0.5 to 1 at % is due mainly to the up-conversion by energy transfer from the pump level and upper laser level. Excited state absorption cannot contribute to depletion of excited states involved in the ³ F ₄-³ H ₆ laser operation near 1800 nm in the YVO₄: Tm crystal. However, the heavy doping required to enhance the cross-relaxation process which feeds the upper laser level brings about the migration-accelerated energy transfer to energy sinks.     

The mechanism of sensitized anti-stokes luminescence in crystals with adsorbed dyes

We have analyzed regular features of sensitization processes of crystals AgCl, AgCl_0.95I_0.05, and Zn_0.6Cd_0.4S to processes of a low-threshold (10^?3–10^?4 W/cm²) two-quantum excitation of anti-Stokes luminescence by adsorbed molecules and by J and H aggregates of dyes of different classes. The excitation centers of this luminescence are complex and consist of dye molecules and few-atom silver clusters adsorbed nearby. Luminescence-excitation processes involve stages of photoexcitation of adsorbed dye molecules; resonance transfer of electronic excitation energy to adsorbed atoms and few-atom silver clusters, levels of which lie near the middle of the band gap; and their subsequent photoionization.     

Continuous wave optically pumped iodine laser: Spectroscopy and long range analysis of the X1Σg+ ground state of I2

Continuous wave oscillation is observed on transitions belonging to the I₂B 0_u⁺-X¹Σ_g⁺ system into highly excited vibrational levels of the ground state. The I₂ laser is optically pumped with a single longitudinal mode argon ion laser oscillating at either 514.5 or 501.7 nm resulting in some 752 assigned laser lines throughout the visible and near infrared. Of these, 44 transitions have 83 ≤ v″ ≤ 96 and are used here to obtain rotational and vibrational constants for levels of X¹Σ_g⁺ near the dissociation limit. A long range analysis applying the theory of LeRoy to the highest observed levels yields C₆ = 1.1 ± 0.1 × 10⁶ cm^?1 Å^?6 and indicates that the last bound vibrational level of X¹Σ_g⁺ has v = 114.     

Spectroscopy of the ClCF radical in solid argon

Study of the ClCF emission and excitation spectra in solid Ar gives values of 392 and 712 cm^?1 for the upper state vibrations ν₂ and ν₃, respectively. The electronic transition has its origin at T₀ = 24 983 cm^?1 and a lifetime of 330 ± 20 nsec. The study of vibrationally unrelaxed emission shows, that intramolecular mode-to-mode energy transfer processes are slow compared to direct multiphonon vibrational relaxation.     

The study of ungerade electronic states of the Xe2 molecules in the region of Xe*(5p 56p, 5d, 7s, 6d) by the resonance multiphoton ionization method

Electronic spectra of the Xe2 molecules in the energy range of 77700?C89300 cm^?1 are recorded. The method of resonance enhanced multiphoton ionization of molecules in a supersonic molecular beam was used, in which excitation of the molecules by three photons was followed by ionization caused by a fourth photon (the (3+1) REMPI method). Analysis of the vibrational structure of observed systems of bands yielded information about the dissociation energy and the molecular constants for ungerade states of molecules. On the basis of the Franck-Condon principle, the equilibrium distances for potential curves were estimated from the relative intensities in vibrational progressions. Data on 16 new electronic states of diatomic xenon molecules with the dissociation limits Xe ₂ ^* ?? XE(5p ^{6 1} S ₀) + Xe*(5p ⁵6p,5d, 7s, 7p) were obtained.     

Vibrationally inelastic scattering of H∼ ions from H2, N2, O2 and CO2

State-resolved measurements are presented for vibrational excitation of H₂, N₂, O₂ and CO₂ by H^? impact in the collision energy rangeE _cm=20–180 eV and for scattering in the forward direction (0±0.5°). The data obtained from the measurements are the relative intensities and differential cross sections for vibrational excitation up toν′=4, the transition probabilitiesP _0→ν′ and the vibrational energy transferΔE _vib. For the systems H^?-H₂, N₂, O₂ the vibrational inelasticity increases in the order H₂-N₂-O₂. The mechanism for vibrational excitation in these systems is due to transient charge transfer from the H^? ion into antibonding orbitals of the target molecule which provides a bond stretching force during the collision. For H₂ and N₂, the results are compared with corresponding measurements for H⁺ scattering where the interaction mechanism is quite different. In the case of CO₂, vibrational excitation in forward scattering is caused primarily by the long-range dipole interaction. The spectra are very similar for H^?-CO₂ and H⁺-CO₂. Finer details are attributed to the influence of transient charge transfer and valence interactions.     

Quenching of the triplet state of Pd-porphyrins by Cu-etioporphyrin in dimethyl formamide

Quenching of phosphorescence of Pd-tetrabenzoporphyrin (Pd-TBP) and Pd-etioporphyrin I (Pd-EP) by the Cu-EP molecules was studied using pulsed photoexcitation. The rate constant of quenching (K _q) by the Cu-EP molecules was found to be 2.3×10⁹ 1/(mol s) for the low lying triplet state (TS) of Pd-Ep and 5.8×10⁸ 1/(mol s) for the TS of Pd-TBP. It is concluded that the quenching was caused by the intermolecular energy transfer, and the low value of K _q for Pd-TBP can be explained by the fact that the level of Cu-EP (X), to which the energy is transferred, lies above the TS of Pd-TBP (E _T=12 900 cm^?1). Based on the results obtained and the published data, it is assumed that the energy transfer proceeds via the formation of long-lived excited complexes of interacting molecules. With the K _q value for Pd-TBP and the results of kinetic analysis of the adopted quenching mechanism, the difference between the energy of states, involved in energy transfer, and the X state energy are determined (E _X=13 520 cm^?1 and E _T=14 500 cm^?1 for Cu-EP). Some specific features of photophysical and luminescence properties of Cu-porphyrins are explained by the presence of such a state related to the excitation of the copper ion.     

A refined potential energy function for the electronic ground state of H2Se

The potential energy surface for the electronic ground state of the hydrogen selenide molecule has been determined previously by Jensen and Kozin [J. Mol. Spectrosc. 160 (1993) 39] in a fitting to experimental data by means of the MORBID computer program. We report here a further refinement of this surface, also made with the MORBID program. With the refined potential surface, we can make predictions of rotation-vibration transition wavenumbers for H₂Se, D₂Se, and HDSe, and with these predictions we can assign weak spectra of these molecules. We assign here two very weak bands of HD⁸⁰Se, ν₁+ν₂+ν₃ and 2ν₁+ν₃. The refinement of the potential energy surface was made possible because (1) the number of vibrational states characterized experimentally for various isotopomers of H₂Se has approximately doubled since 1993, and (2) we now have access to larger computers with which we can fit energy spacings of states with J?8, whereas Jensen and Kozin could only use J?5. In the present work, we fitted rotation-vibration energy spacings associated with 24 vibrational states of H₂⁸⁰Se with v₁?6, v₂?3, and v₃?2; 11 vibrational states of D₂⁸⁰Se with v₁?2, v₂?3, and v₃?2, and 17 vibrational states of HD⁸⁰Se with v₁?3, v₂?3, and v₃?3. The input data set comprised 3611 energy spacings. In the fitting, we could usefully vary 29 potential energy parameters. The standard deviation of the fitting was 0.12 cm⁻¹ and the root-mean-square deviation for 49 vibrational term values was 0.59 cm⁻¹.