Lattice relaxation and charge-transfer optical transitions due to self-trapped holes in nonstoichiometric LaMnO3 crystal

We explore the role of electronic and ionic polarization energies in the physics of “colossal” magnetoresistive (CMR) materials. We use the Mott-Littleton approach to evaluate polarization energies in the LaMnO₃ lattice associated with holes localized on both the Mn³⁺ cation and the O^2?anion. The full (electronic and ionic) lattice relaxation energy for a hole localized at the O site is estimated at 2.4 eV, which is appreciably greater than that of 0.8 eV for a hole localized at the Mn site, indicating a strong electron-phonon interaction in the former case. The ionic relaxation around the localized holes differs for anion and cation holes. The relaxation associated with Mn⁴⁺ is approximately isotropic, whereas ionic displacements around O^? holes show axial symmetry with the axis directed towards the apical oxygens. Using the Born-Haber cycle, we examine thermal and optical energies of the hole formation associated with the electron ionization from Mn³⁺, O^2?, and La³⁺ions in the LaMnO₃ lattice. For these calculations, we derive a phenomenological value for the second electron affinity of oxygen in the LaMnO₃ lattice by matching the optical energies of the La⁴⁺ and O^? hole formation with maxima of binding energies in the experimental photoemission spectra. The calculated thermal energies predict that the electronic hole is marginally more stable in the Mn⁴⁺ state in the LaMnO₃ host lattice, but the energy of a hole in the O^? state is only higher by a small amount, 0.75 eV, suggesting that both possibilities should be treated seriously. We examine the energies of a number of fundamental optical transitions, as well as those involving self-trapped holes of Mn⁴⁺ and O^? in the LaMnO₃ lattice. The reasonable agreement of our predicted energies, linewidths, and oscillator strengths with experimental data leads us to plausible assignments of the optical bands observed. We deduce that the optical band near 5 eV is associated with the O(2p)-Mn(3d) transition of a charge-transfer character, whereas the band near 2.3 eV is rather associated with the presence of Mn⁴⁺ and/or O^? self-trapped holes in the nonstoichiometric LaMnO₃ compound.     

Luminescence study of self-trapped holes in pure and Fe- or Mo-doped ZnWO4 crystals

Thermostimulated and photostimulated luminescence of ZnWO₄, ZnWO₄:Fe and ZnWO₄:Mo crystals irradiated at low temperatures by X-rays or UV photons was studied in the temperature range 4.2–300 K in order to clarify the creation and recombination processes of the elementary colour centres. The connection of the luminescence phenomena with the self-trapped holes has been revealed.     

Suppression of the local Jahn-Teller effect in nanostructures: Self-trapped holes and excitons in AgCl nanocrystals

A strong decrease in the g-factor anisotropy was revealed by optically detected magnetic resonance for self-trapped Jahn-Teller holes (both isolated and forming self-trapped excitons) in AgCl nanocrystals embedded into the KCl crystal lattice. This is evidence for considerable suppression of the Jahn-Teller effect in nanoobjects. The suggested mechanism of suppression of the Jahn-Teller effect in nanocrystals is associated with an additional deformation field arising in nanocrystals owing to a strong vibronic interaction at the interface.     

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.     

Two-photon spectroscopy in AgCl

Two-photon absorption constant β⁽²⁾ has been measured in the indirect gap of AgCl between 4 and 4.4 eV. The absorption constant has been derived from the excitation spectrum of the recombination luminescence. The absolute value of β⁽²⁾ is in fair agreement with that calculated for a two-photon phonon-assisted transition.     

Stimulated self-trapped exciton emission in CsI:Pb

Defects of the type of V_K and Pb⁺ centres were created in CsI:Pb under the 4.03 eV XeCl laser line irradiation at 10 K. After irradiation, the self-trapped and localized exciton emission excited by the same XeCl laser line was observed as a result of the recombination of electrons, optically released from Pb⁺, with the V_K centres. A strongly superlinear dependence of the emission intensity on the excitation intensity was found for the 3.65 eV emission of the self-trapped exciton. A much weaker superlinearity was observed for the visible localized exciton emission. Optical amplification of the exciton emission was considered as the most probable reason of the observed phenomenon. At 10 K, optical gain G=3.74 was calculated for the self-trapped exciton emission.     

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.     

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.     

Femtosecond study of self-trapped vibrational excitons in crystalline acetanilide

Femtosecond IR spectroscopy of delocalized NH excitations of crystalline acetanilide confirms that self-trapping in hydrogen-bonded peptide units exists and does stabilize the excitation. Two phonons with frequencies of 48 and 76 cm (-1) are identified as the major degrees of freedom that mediate self-trapping. After selective excitation of the free exciton, self-trapping occurs within a few 100 fs. Excitation of the self-trapped states disappears from the spectral window of this investigation on a 1 ps time scale, followed by a slow ground state recovery of the hot ground state within 18 ps.     

Theory of the self-trapped paramagnetic spin polaron

The self-trapped spin polaron is studied for a purely paramagnetic crystal in the limit of an extremely dilute system of carriers. A Zubarev-Green-function decoupling scheme is used. Owing to spin-flip processes the trapping potential for the spin polaron is shown to vanish as the width of the conduction band,E _b, becomes small compared with thes?f ors?d exchange constant,I. ForE _b?I our results agree with those of Kasuyaet al. In the opposite limit of a degenerate system of carriers the term that leads to trapping in the dilute case is shown to become the RKKY indirect-exchange interaction.     

Absorption spectra of self-trapped exciton in condensed rare gases

Optical absorption from the self-trapped exciton (STE) to its higher excited states has been observed in solid Ar, Kr, and Xe. A new absorption peak of Ar1₂ is found. Comparison of solid, liquid and gas phase data provides evidence of the similarity of level structures of Ar1₂ and STE. Tentative assignments of the observed transitions are also made.     

Luminescence decay in AgCl crystals

The kinetics of luminescence decay of single crystal plates of AgCl was measured at the temperature of liquid nitrogen. Luminescence decay first takes place (fort≦2·5× ×10^?3 sec) according to a hyperbole and then according to an exponential. The constantsa anda of the hyperbolic andt of the exponential dependence were measured for different intensity of the exciting radiation in normal and deformed samples and in samples irradiated withb-particles during measurement.