Luminescence study of self-trapped excitons in CdMoO4

Luminescence properties of CdMoO₄ crystals have been investigated in a wide temperature range of T=5–300 K. The luminescence-excitation spectra are examined by using synchrotron radiation as a light source. A broad structureless emission band appears with a maximum at nearly 550 nm when excited with photons in the fundamental absorption region (<350 nm) at T=5 K. This luminescence is ascribed to a radiative transition from the triplet state of a self-trapped exciton (STE) located on a (MoO₄)^2? complex anion. Time-resolved luminescence spectra are also measured under the excitation with 266 nm light from a Nd:YAG laser. It is confirmed that triplet luminescence consists of three emission bands with different decay times. Such composite nature is explained in terms of a Jahn–Teller splitting of the triplet STE state. The triplet luminescence at 550 nm is found to be greatly polarized in the direction along the crystallographic c axis at low temperatures, but change the degree of polarization from positive to negative at T>180 K. This remarkable polarization is accounted for by introducing further symmetry lowering of tetrahedral (MoO₄)^2? ions due to a uniaxial crystal field, in addition to the Jahn–Teller distortion. Furthermore, weak luminescence from a singlet state locating above the triplet state is time-resolved just after the pulse excitation, with a polarization parallel to the c axis. The excited sublevels of STEs responsible for CdMoO₄ luminescence are assigned on the basis of these experimental results and a group-theoretical consideration.     

Singlet-triplet splittings in free and self-trapped excitons

We discuss the available experimental data for the singlet-triplet splitting of free and self-trapped excitons in alkali halides. These data are analysed quantitatively using the pseudopotential method of Bartram, Stoneham and Gash. The predictions confirm the trend emerging from the observed data, namely that the splittings are systematically lower for the self-trapped systems. This difference comes principally from the spread of the self-trapped hole onto two ions, and would not be expected, for example, if the hole were localised on a single site.     

Excitons perturbed by self-trapped excitons in alkali iodine crystals

A strong transient optical absorption band on the exciton shoulder has been observed in pure alkali iodine crystals following pulsed electron irradiation. The ultraviolet transition is ascribed to creation of a second exciton in the vicinity of a self-trapped exciton. The perturbation caused by the proximity of the self-trapped exciton lowers the energy needed to form the second exciton by 0.14 eV for KI and 0.12 eV for RbI.     

Real-time capturing of the nuclear wave-packet shape in self-trapped excitons

We measured the time evolutions of the luminescence spectra in a quasi-1D halogen-bridged platinum complex [Pt(en)(2)][Pt(en)(2)Br(2)](ClO4)(4) with a 50 fs resolution up-conversion spectroscopy and succeeded in real-time visualization of the shape of the wave packet (WP) propagating on the adiabatic potential surface of a self-trapped exciton. The behavior of the WP is in excellent agreement with a calculation based on a harmonic oscillator. We have found that the damping of the WP oscillation is highly nonexponential.     

A time-resolved luminescence spectroscopy study of self-trapped excitons in KH2PO4 crystals

A complex investigation of the dynamics of electronic excitations in potassium dihydrophosphate (KDP) crystals is performed by the low-temperature time-resolved vacuum ultraviolet optical luminescence spectroscopy with subnanosecond time resolution and with selective photoexcitation by synchrotron radiation. For KDP crystals, data on the kinetics of the photoluminescence (PL) decay, time-resolved PL spectra (2–$\text{6.2}\text{eV}$), and time-resolved excitation PL spectra (4–$\text{24}\text{eV}$) at $\text{10}\text{K}$ were obtained for the first time. The intrinsic character of the PL of KDP in the vicinity of $\text{5.2}\text{eV}$, which is caused by the radiative annihilation of self-trapped excitons (STEs), is ascertained; σ and π bands in the luminescence spectra of the STEs, which are due to singlet and triplet radiative transitions, are resolved; and the shift of the σ band with respect to the π band in the spectra of the STEs is explained.     

Direct observation of self-trapped vibrational states in alpha-helices

Femtosecond infrared pump-probe spectroscopy of the N-H mode of a stable alpha-helix reveals two excited-state absorption bands, which disappear upon unfolding of the helix. A quantitative comparison with polaron theory shows that these two bands reflect two types of two-vibron bound states connected to the trapping of two vibrons at the same site and at nearest neighbor sites, respectively. The latter states originate from an acoustic phonon in the helix, which correlates adjacent sites.     

Semiclassical and quantum polarons in crystalline acetanilide

Crystalline acetanilide is a an organic solid with peptide bond structure similar to that of proteins. Two states appear in the amide I spectral region having drastically different properties: one is strongly temperature dependent and disappears at high temperatures while the other is stable at all temperatures. Experimental and theoretical work over the past twenty five years has assigned the former to a selftrapped state while the latter to an extended free exciton state. In this article we review the experimental and theoretical developments on acetanilide paying particular attention to issues that are still pending. Although the interpretation of the states is experimentally sound, we find that specific theoretical comprehension is still lacking. Among the issues that that appear not well understood is the effective dimensionality of the selftrapped polaron and free exciton states.     

Luminescence of self-trapped excitons in calcium fluoride under pulsed electron irradiation

Time-resolved pulsed spectroscopy was used to measure the luminescence spectra of calcium fluoride. Characteristic features of the luminescence of self-trapped excitons are discussed. It is shown that various configurations of self-trapped excitons incorporating hole nuclei of a more complex structure, may be formed in CaF₂ crystals. Fiz. Tverd. Tela (St. Petersburg) 40, 1226–1227 (July 1998)     

On the nature of emission bands of self-trapped excitons in solid xenon

The paper presents the analysis of experimental data on the temperature dependence of luminescence spectra of solid xenon. The mechanisms of exciton self-trapping down to quasi-molecular states under different conditions are discussed. A new treatment of spectral distribution of intensity through quasi-molecular luminescence bands is proposed; according to the treatment, at T < 55 K the emission is associated with the transition from the lowest vibrational relaxation excited state ³Σ_u⁺, while at T 60 K from the term ¹Σ_u⁺. Spectral redistribution of intensities in the 60–150 K range is due to an increase in the rate of vibrational relaxation in the state ¹Σ_u⁺ with increasing the crystal temperature.     

Evolution of Frenkel pairs from excited states of self-trapped excitons in alkali halides

We find that the transition to the first and second electron excited states from the lowest self-trapped excitons in KCl and RbCl are π- and σ-polarized, respectively. For KCl the orientation of the H centers evolved from the self-trapped exciton by exciting to these states are shown to be in parallel to the orientation of the self-trapped excitons.     

Conversion ratio to F-H center pairs from self-trapped excitons in alkali chloride crystals

Abstract

The time delayed double excitation spectroscopy has been utilized to determine the conversion ratio to F-H center pairs from self-trapped excitons(STE_L) at the lowest state (1s[sgrave]_g;a_1g). The final conversion ratios, η_F/(η_F+η_X), were 0.86, 0.49 and 0.20 for NaCl, KCl and RbCl at 14K, respectively. The conversion efficiency (η =η_F+η_X) from STE_L to F-H center pairs(η_F) and to unknown states(η_X) were 0.25, 0.90 and 0.76 for the hole excitation to π_g, while 0.03, 0.01 and 0.01 for the electron excitation to b_1u, b_2u or b_3u, in NaCl, KCl and RbCl, respectively.     

Time-resolved spectroscopy of self-trapped excitons in fluorides of alkaline-earth metals under pulsed electron irradiation

Nanosecond-resolution absorption spectroscopy at room temperature was used to study the laws governing the creation and evolution of the primary defect structure in CaF₂, SrF₂, and BaF₂ crystals exposed to an accelerated electron pulse. It is shown that the spectral-kinetic characteristics of self-trapped excitons created in undamaged parts of the crystal lattice are qualitatively similar. Partial polarization of the absorption of self-trapped excitons is observed in CaF₂. The structure of the transient absorption spectra becomes more complex in the sequence CaF₂, SrF₂, BaF₂ because of the formation of excitons trapped in phase inclusions of homologous cationic impurities. The spectral characteristics of excitons trapped in undamaged parts of the CaF₂ and SrF₂ lattice and in their phase inclusions in BaF₂ are the same although the latter have a considerably shorter relaxation time. Short-lived (τ⩽100 ns) absorption of unknown defects was observed in the spectral range ⩾5 eV. Fiz. Tverd. Tela (St. Petersburg) 40, 1228–1234 (July 1998)     

The role of self-trapped excitons and defects in the formation of nanogratings in fused silica

We investigate the role of self-trapped excitons (STEs) and defects in the formation of femtosecond laser pulse induced nanogratings (NGs) in fused silica. Our experiments reveal strongly enhanced NG formation for pulse separations up to the STE lifetime. In addition, the absorption spectra show that the weaker cumulative action of laser pulses for longer temporal separations is predominantly mediated by dangling-bond-type lattice defects that emerge from decaying STEs.     

The temperature dependent amide I band of crystalline acetanilide

The temperature dependent anomalous peak in the amide I band of crystalline acetanilide is thought to be due to self-trapped states. On the contrary, according to the present model, the anomalous peak comes from the fraction of ACN molecules strongly hydrogen-bonded to a neighboring ACN molecule, and its intensity decreases because, on average, this fraction decreases as temperature increases. This model provides, for the first time, an integrated and theoretically consistent view of the temperature dependence of the full amide I band and a qualitative explanation of some of the features of nonlinear pump–probe experiments.