Pseudolocal Phonons Research Articles

Fine structure of another blue luminescence band in undoped GaN

A blue luminescence band, labeled BL3, has been found in undoped GaN samples grown by hydride vapor phase epitaxy. It has a maximum at 2.8 eV and a phonon-related fine structure at its high-energy side. The zero-phonon line of this band consists of a duplet with two sharp lines at 3.0071 and 3.0147 eV. Three phonon modes, including the LO mode with an energy of 91.3 meV and two pseudolocal phonon modes with energies of 39.6 and 68.2 meV, form the characteristic fine structure of the BL3 band. The BL3 band is attributed to internal transitions from excited states located near the conduction band to the 0/+ transition level of unknown defect. The defect is preliminarily identified as the RY3 center, which is also responsible for bright red-yellow luminescence bands in the studied samples.

Two yellow luminescence bands in undoped GaN

Two yellow luminescence bands related to different defects have been revealed in undoped GaN grown by hydride vapor phase epitaxy (HVPE). One of them, labeled YL1, has the zero-phonon line (ZPL) at 2.57 eV and the band maximum at 2.20 eV at low temperature. This luminescence band is the ubiquitous yellow band observed in GaN grown by metalorganic chemical vapor deposition, either undoped (but containing carbon with high concentration) or doped with Si. Another yellow band, labeled YL3, has the ZPL at 2.36 eV and the band maximum at 2.09 eV. Previously, the ZPL and fine structure of this band were erroneously attributed to the red luminescence band. Both the YL1 and YL3 bands show phonon-related fine structure at the high-energy side, which is caused by strong electron-phonon coupling involving the LO and pseudo-local phonon modes. The shapes of the bands are described with a one-dimensional configuration coordinate model, and the Huang-Rhys factors are found. Possible origins of the defect-related luminescence bands are discussed.

Molecular Simulation of the Pressure-Induced Crystallographic Phase Transition of p-Terphenyl

The pressure- and temperature-induced polymorphic crystal phase transitions of p-terphenyl (PTP) have been modeled using a modified PCFF interaction force field. Modifications of the interaction potential were necessary to simultaneously model both the temperature-induced phase transition at ambient pressure and the pressure-induced phase transition at low temperature. Although the high-temperature and high-pressure phases are both characterized by flattening of the PTP molecule, the mechanisms of the temperature- and pressure-induced phase transitions are different. At high temperature thermal energy exceeds the torsional barrier, resulting in a bimodal phenyl ring twist angle distribution that averages to zero. In contrast, compression of PTP at high pressure results in a static planar structure. At high pressure the compression of the unit cell is also characterized by large compression of the a lattice parameter and weak compression of c, but some expansion of the b lattice parameter. The expansion of the b lattice parameter is likely associated with pressure-induced soft mode behavior of some lattice vibrations as well as soft mode behavior of pseudolocal phonons associated with impurities in PTP. The crystallographic angles α, β, and γ also indicate a triclinic crystal phase above the critical phase transition pressure of P(c) ~ 0.5 GPa at low temperature, suggesting a distinct phase separate from the monoclinic high-pressure phase at high temperature.

Anharmonic Electron−Phonon Coupling in Condensed Media: 2. Application to Electronic Dephasing, Hole-Burning, and Photon Echo

While different expressions of homogeneous linear electronic dipole moment time correlation functions and their respective absorption lineshapes of anharmonic systems were derived and discussed at length in part I [Toutounji, M. J. Phys. Chem. B 2010, in press] of this study, the electronic dephasing (zero-phonon line width), caused by pseudolocal phonons, and vibrational relaxation time scales were treated equally, hence, unphysical. In this study electronic dephasing and vibrational structure are correctly accounted for in harmonic and anharmonic multimode systems. Model calculations are presented. Anharmonic hole-burned spectra are calculated using linear anharmonic absorption lineshapes. An analytical expression of hole-burned absorption line shape in terms of the linear dipole moment time correlation function, leading to a hole-burned absorption line shape expressed in time-domain, is reported. An elementary method is utilized to treat nonlinear spectra in anharmonic molecules. The link between a hole-burned spectrum and a 2-pulse photon echo profile is established by combining the theoretical framework of Mukamel and that of Hays-Small, thereby calculating photon echo signals of anharmonic systems. Model photon echo calculations of a solvable harmonic model and an anharmonic system are reported. Applications to Al-phthaolcyanine tetrasulphonate (APT) in hyperquenched glassy ethanol and special pair bacterial reaction center are presented and discussed in detail.

Superradiance regime of laser cooling in extended solids

The kinetics of the extended crystal doped by rare-earth ions in the regime of anti-Stokes laser cooling has been considered taking into account the collective radiation effects. The system of Markovian equations for impurities and pseudolocal phonons has been obtained. As would be expected, the collective radiation effects cause an acceleration in relaxation depletion of the phonon mode and, therefore, an increase in crystal cooling efficiency.

Time-resolved coherent anti-Stokes Raman-scattering measurements of I2 in solid Kr: Vibrational dephasing on the ground electronic state at 2.6–32 K

Time-resolved coherent anti-Stokes Raman-scattering (CARS) measurements are carried out for iodine (I2) in solid krypton matrices. The dependence of vibrational dephasing time on temperature and vibrational quantum number v is studied. The v dependence is approximately quadratic, while the temperature dependence of both vibrational dephasing and spectral shift, although weak, fits the exponential form characteristic of dephasing by pseudolocal phonons. The analysis of the data indicates that the frequency of the pseudolocal phonons is approximately 30 cm(-1). The longest dephasing times are observed for v = 2 being approximately 300 ps and limited by inhomogeneous broadening. An increase in the dephasing rate of v = 2 as the temperature is lowered to T = 2.6 K is taken as a clear indication of lattice-strain-induced inhomogeneity of the ensemble coherence.

Dynamics of phonon mode in superradiance regime of laser cooling of crystals

The kinetics of the impurity crystal in regime of anti-Stokes laser cooling has been considered taking into account the collective radiation effects. The system of master equations for impurities and pseudo-local phonons has been obtained. As would be expected, the collective radiation effects causes an acceleration in relaxation depletion of the phonon mode and therefore an increase of crystal cooling efficiency.

Vibrational dissipation and dephasing of I2(v = 1–19) in solid Kr

Time- and frequency-resolved coherent anti-Stokes Raman scattering is used to carry out systematic measurements of vibrational dephasing on I2 (v = 1-19) isolated in solid Kr, as a function of temperature, T = 7-45 K. The observed quantum beats, omega(v', v") allow an accurate reconstruction of the solvated molecular potential, which is well represented by the Morse form: omega(e) = 211.56 +/- 0.14, omega(e)chi(e) = 0.658 +/- 0.006. Near T = 7 K, the coherence decay rates gamma(v,0) become independent of temperature and show a linear v-dependence, indicative of dissipation, which must be accompanied by the simultaneous creation of at least four phonons. At higher temperatures, the T-dependence is exponential and the v-dependence is quadratic, characteristic of pure dephasing via pseudo-local phonons. A normal mode analysis suggests librations as the principle modes responsible for pure dephasing.

Time-resolved CARS measurements of the vibrational decoherence of I2 isolated in an Ar matrix

Time-resolved coherent anti-Stokes Raman scattering is applied to prepare and interrogate vibrational coherences on the ground electronic surface of molecular iodine isolated in Ar matrices. The coherence decay time shows a linear dependence on vibrational quantum numbers for v=3–15. The temperature dependence of decoherence rates is negligible for v<7 in the experimental range T=18–32 K. For a v=13, 14 superposition, the temperature dependence indicates dephasing by a 66 cm−1 pseudo-local phonon, just outside the Debye edge of the solid. The accuracy of the data is limited due to two-photon induced dissociation of the molecule, a process which is characterized using polarized fields. The T→0 limit of dephasing is discussed.

Non-lorentzian single-molecule line shape: pseudolocal phonons and coherence transfer

The excitation line shape of a single terrylene molecule in a naphthalene crystal has been investigated. In addition to the conventional Lorentzian, it consists of a dispersive component in the core region and a sideband. This is due to a pseudolocal phonon caused by the substitution of a host molecule with the chromophore. When the pseudolocal phonon is excited, the resonance frequency of the chromophore slightly changes, resulting in the appearance of a second, quasiresonant transition. Coherence transfer between these two optical transitions causes the deviation from the purely Lorentzian line shape.

Persistent spectral hole-burning in a -doped aluminosilicate glass from 8 to 295 K: Study of the burning and refilling kinetics, and of optical dephasing

High-temperature persistent spectral hole-burning (PSHB), up to room temperature, has been observed in a Eu 3+ -doped aluminosilicate glass using a high peak-power nanosecond dye laser. Spontaneous refilling as well as thermal cycling measurements show that at least two mechanisms, a fast and a slow one, are involved in our sample. We suggest that the fast or “easy” component may correspond to a non-photochemical local rearrangement of the host or to photoreduction of the Eu 3+ ions and that the second one leading to very stable photoproducts may correspond to transfer of an electron over a sizable distance through a several-step process. The mechanisms we suggest agree with light-induced hole refilling measurements. Line broadening mechanisms are discussed and the temperature-dependent part of the homogeneous width and of the spectral shift is interpreted in terms of a two-phonon (Raman) process involving pseudo-local phonons.

Probing the spectral dynamics of single terrylenediimide molecules in low-temperature solids

Fluorescence excitation lines of single terrylenediimide (TDI) molecules were recorded in the matrices polyethylene (PE) and hexadecane (HD) in the temperature range between 1.4 and 13 K. From line width distributions at 2.5 K in both matrices it was concluded that the disorder, theoretically modeled by a distribution of two-level systems (TLSs), is about three times stronger in PE. Temperature-dependent measurements of the line shape of single chromophores showed a reversible broadening and shift of the zero-phonon lines. We attributed this behavior to dephasing caused by pseudolocal phonons and to spectral diffusion caused by fluctuating TLSs of the disordered host. Following these assumptions, the data could be well approximated with the pertinent expressions. The specific environments of the individual molecules are reflected by different behaviors of their `homogeneous' lines.

Temperature-dependent line broadening of chromophores in amorphous solids: Differences between single-molecule spectroscopy and photon echo results

Spectroscopic techniques exhibit different sensitivities for line broadening processes in amorphous solids. Photon echo and hole-burning spectroscopy yield averages over the chromophore ensemble. At low temperatures, the results can usually be fitted with a combination of a power-law term — corresponding to the relaxations of two-level systems- and of an exponentially activated contribution of pseudo-local phonon modes. Single-molecule spectroscopy (SMS). in contrast, can resolve the behavior of single dye molecules and yields a distribution of power laws as well as of activation energies. We compare photon echo results for tetra-tert-butylterrylene (TBT) in polyisobutylene (PIB) with SMS data for the same system. The latter were used to simulate numerically the data which would be obtained in an ensemble-averaging experiment. The results of the numerical calculation can be well fitted without assuming a distribution of parameters.

Single Molecule and Shpolskii Spectroscopy of Terrylene in a Series of N-Alkanes

Abstract We present a study of terrylene in a series of n-alkane matrices with increasing chain length, namely dodecane, tetradecane and hexadecane. Shpolskii absorption spectra provide the macroscopic characterization of the samples, such as site multiplicity, inhomogeneous line widths and positions. Based on this characterization the distributions of single molecule homogeneous line widths were measured in the maxima and in the wings of the inhomogeneous lines. The results indicate that in case of dodecane matrix the line broadening is caused by optical dephasing due to interaction with pseudolocal phonon modes. Exponential profile of temperature dependence of the line width gives the phonon energy of 23 cm−1. In cases of tetradecane and hexadecane matrices there is additional broadening present which we interpret as spectral diffusion. Further, we present a new method for collecting the single molecule fluorescence using a selfoc micro lens.

A photon echo study of pentacene in naphthalene at high pressure

Temperature-dependent (2–10 K) photon echo measurements are presented for pentacene in naphthalene at high pressure (12.5 kbar) in a diamond anvil cell. A decrease in the homogeneous dephasing rate (i.e. a narrowing of the homogeneous linewidth) is observed at high pressure. In addition, the temperature dependence of the homogeneous dephasing rate is used to obtain the effect of pressure on the frequency and lifetime of the pseudolocal phonon associated with a pentacene impurity in a crystalline naphthalene matrix.

Pseudolocal phonons in p-terphenyl: pentacene single crystals

The structural nature of the phonon sidebands in the fluorescence and excitation spectra of pentacene guests in p-terphenyl crystals at 4.2 K are investigated using site-selective spectroscopy. The distinct features in the phonon sideband structure were observed to depend significantly on the guest site configuration of pentacene occupying four inequivalent sites in the triclinic p-terphenyl lattice. The sharp peaks dominating the phonon sideband structure are assumed to arise from the pseudolocal phonons. The eigenvalues and eigenvectors of the pseudolocal phonons are calculated carrying out a modified normal mode analysis on the distinct pentacene site configurations including the contribution of all intermolecular atom-pair interactions.

Solute-solvent dynamics and interactions in glassy media: Photon echo and optical hole burning studies of cresyl violet in ethanol glass

Photon echo and non-photochemical hole burning experiments on cresyl violet in ethanol glass are reported. At 1.5 K the optical dephasing time measured by the picosecond echo is eight times longer than the time measured by hole burning because of the difference in the time scales associated with the measurements. The observed temperature dependence arises from the glass's two-level systems and from a pseudolocal phonon mode at higher temperatures. Comparing the ratios of the echo to hole burning dephasing times for cresyl violet and resornfin, suggests that their dephasing is influenced by the nature of their ethanol solvation shells in addition to the dynamics of the bulk ethanol.

Optical and vibrational dephasing in crystals: Theory and experiment

The linewidths of both optical and vibrational transitions in crystals are often dominated by adiabatic coupling to phonons. We have recently developed a nonperturbative theory of dephasing due to the above, and have considered models for coupling to acoustic, optical, and pseudolocal phonons. We apply our theoretical results to optical experiments on NaF:Cu + by Pack and McClure, and to vibrational experiments on the 766 cm -1ϵ 8 mode of pure naphthalene by Hess and Prasad and Schosser and Dlott.

Pure dephasing and nonradiative decay processes in the excited electronic states of NaF:Cu+

We report the first optical dephasing study of an inorganic impurity system possessing sharp, low frequency mode structure in its ground and excited state spectra. The total dephasing times T2 and population relaxation times T1 for the 1T2g and 1Eg d9s excited states of NaF:Cu+ are determined at a series of temperatures between 1.8 and 296 K. The T2 values are determined by extracting the Lorentzian components from one- and two-photon excitation line shapes. The T1 values caused by nonradiative decay rates are obtained by detecting very low quantum yield emission from the fast-relaxing excited states and applying the formula tnr=Qtr, where t’s are radiative and nonradiative lifetimes and Q is the quantum yield. T1(1T2g)=4.6 ps and T1(1Eg )=2.0 ps at 8 K. Significantly, these are very similar to the T1 values calculated from lowest temperature Lorentzian linewidths by the relationship 1/T2=1/T′2 +1/(2T1). The T1 values stay approximately constant over the temperature range 1.8–45 K, while the linewidths rapidly increase indicating that pure dephasing dominates. Using ground and excited state information on the low frequency modes, we test optical Redfield theory and the nonperturbative harmonic theory for pure dephasing by pseudolocal phonons against data for this system which displays strongly anhamonic progressions. The nonperturbative theory fits the line broadening data to higher temperatures than optical Redfield theory for the least anharmonic excited state potential, 1T2g. Both theories underpredict the broadening with temperature of the extremely anharmonic 1Eg state. A simple anharmonic theory including scattering to overtone levels also fails to predict the observed linewidth temperature behavior, although it is demonstrated these processes should be occurring.

Nonperturbative theory of temperature-dependent optical dephasing in crystals. IV. Microscopic model for pseudolocal phonons

We continue our study of the optical dephasing of impurities by phonons. The pure dephasing contribution to the homogeneous linewidth is calculated to all orders in the excitation–phonon interaction. We introduce a microscopic model for the pseudolocal phonon spectral density when the impurity is in the ground electronic state. This microscopic model improves upon our previous phenomenological model. The model is applied to several experimental systems—in all cases, the theoretical results provide a reasonably accurate description of the temperature-dependent linewidth with no adjustable parameters.