Yuri G. Vainer

Levy Statistics for Random Single-Molecule Line Shapes in a Glass

We demonstrate that the statistical behavior of random line shapes of single tetra-tert-butylterrylene chromophores embedded in an amorphous polyisobutylene matrix at T=2 K is described by Lévy statistics as predicted theoretically by Barkai, Silbey, and Zumofen [Phys. Rev. Lett. 84, 5339 (2000)]. This behavior is a manifestation of the long-range interaction between two-level systems in the glass and the single molecule. A universal amplitude ratio is investigated, which shows that the standard tunneling model assumptions are compatible with the experimental data.

Moments of single-molecule spectra in low-temperature glasses: Measurements and model calculations

Single-molecule spectroscopy of isolated chromophores in solids yields detailed information about the matrix on a microscopic level. In most studies so far, single-molecule (SM) spectra have been characterized by their linewidths. We demonstrate that in a doped amorphous polymer, in which SM excitation spectra generally have a complicated shape, the shapes of SM lines are more fully characterized by their moments than by the usually used linewidth. We present the measured and simulated distributions of the first four moments and of the linewidth for low-temperature spectra of single tetra-tert-butylterrylene molecules embedded in an amorphous poly(isobutylene) matrix. The simulations are based on the standard tunneling model of glasses with appropriate modifications and on a theory of SM line shapes in a disordered host, which was recently derived by Geva and Skinner [J. Phys. Chem. B 101, 8920 (1997)]. The comparative analysis of the measured and simulated distributions allowed us to evaluate the minimal...

Dynamics of a doped polymer at temperatures where the two-level system model of glasses fails: Study by single-molecule spectroscopy

We investigated the spectra of a large number of single tetra-tert-butylterrylene molecules embedded in an amorphous polyisobutylene matrix and analyzed the distributions of their linewidths (widths of single spectral peaks). The measurements were performed at 2, 4.5, and 7 K. This is a temperature region, where the standard two-level system (TLS) model of low-temperature glasses begins to fail. At T=2 K the temporal behavior (history of frequency jumps) of most of the measured spectra and their linewidth distributions were found to be consistent with the TLS model. At higher temperatures the main features of individual spectra (number of spectral peaks, temperature variation of peak widths, ratio of intensities of different peaks, etc.) still appear consistent with the predictions of this model. An increase of temperature leads mainly to the broadening of spectral peaks. A detailed analysis of the linewidth distributions reveals deviations from a standard TLS model at T=4.5 and 7 K. This difference is at...

Dispersion of the local parameters of quasilocalized low-frequency vibrational modes in a low-temperature glass : Direct observation via single-molecule spectroscopy

Spectra of single tetra-tert-butylterrylene chromophore molecules embedded in an amorphous polyisobutylene matrix as microprobes were recorded. The individual temperature dependences of the spectral linewidths for the same single molecules (SMs) in a broad temperature interval (1.6 < T < 40 K) have been measured. This enabled us to separate the contributions of tunneling two-level systems and quasilocalized low-frequency vibrational modes (LFMs) to the observed linewidths. The analysis of the T dependences yields the values of LFM frequencies and SM-LFM coupling constants for the LFMs in the local environment of a given chromophore. Pronounced distributions of the observed parameters of LFMs were found. This result can be regarded as the first direct experimental proof of the localized nature of LFMs in glasses.

Low-Temperature Dynamics of Amorphous Polymers and Evolution over Time of Spectra of Single Impurity Molecules: I. Experiment

The optical dynamics of a doped amorphous system, tetra-tert-butylterrylene in amorphous polyisobutylene, has been experimentally studied by the spectra of single impurity molecules measured at temperatures of 2, 4.5, 7, and 15 K. The study of the temporal evolution of the fluorescence excitation spectra of the molecules under consideration made it possible to unambiguously establish the individual identity of the spectra of particular molecules and to analyze their multiplet structure. Repeated scanning of a selected spectral range with subsequent summation of the data made it possible to considerably reduce the errors that arise upon single scanning of the spectra of single molecules. The majority of the spectral trails detected were in agreement with the model of two-level systems. Jumps of spectral lines due to transitions in such systems were observed at all temperatures.

Low-temperature dynamics of amorphous polymers and evolution over time of spectra of single impurity molecules: II. Model calculations and analysis of results

The results of a statistical analysis of the spectra of single molecules of tetra-tert-butylterrylene in amorphous polyisobutylene at temperatures of 2, 4.5, and 7 K are presented. Model calculations of such spectra for this system are performed in the context of the stochastic theory of the spectra of single molecules in lowtemperature glasses. Analysis of the multiplet structure of the experimental and model spectra made it possible to obtain data about the minimal distance between impurity chromophore molecules and two-level systems and about the distribution parameters of their coupling constant. The interaction of a chromophore with quasilocal low-frequency vibrational modes of the matrix was found to influence the structure and parameters of the spectra observed. The model calculations performed showed that the specific structure of the spectra of single molecules at low temperatures is determined by the interactions with a small number of nearby two-level systems.

Spectrally resolved analysis of fluorescence blinking of single dye molecules in polymers at low temperatures

We present a method for the spectrally resolved analysis of fluorescence blinking of single quantum emitters. It is based on the well-known technique of repeated recording of single-molecule (SM) fluorescence excitation spectra. The potential of our approach is presented for the example of single tetra-tert-butylterrylene molecules in an amorphous polymer matrix (polyisobutylene), which exhibit fluorescence blinking at cryogenic temperatures. Measuring the spectral dependence of the blinking statistics improves the possibility to clarify the microscopic nature of the dark state(s) of the emitters. We demonstrate how the blinking statistics can be definitely attributed to conformational changes in the local environment of a SM and how the parameters of the corresponding elementary excitations can be measured. The analysis of the blinking statistics as a function of the optical excitation frequency allows us to discriminate between photo-induced and spontaneous transitions into a dark state.

Thermal Activation of Two-Level Systems in a Polymer Glass as Studied with Single-Molecule Spectroscopy

Fluorescence excitation spectroscopy of single chromophores in an amorphous polymer at low temperatures allows the study of single two-level systems (TLSs) of the matrix. With increasing temperature, more TLSs are thermally activated and contribute to random flipping, splitting, and/or broadening of single-molecule lines. In this paper we report on temperature-dependent changes of the intensity ratio between different components of single-molecule lines. The system under study is tetra-tert-butyl-terrylene in poly-isobutylene. Since the temperature dependent changes are due to thermal activation of individual TLSs, we could calculate the asymmetry of several of these TLSs yielding values between 0.25 and 1.5 meV. Some of the TLSs do not follow the Boltzmann activation law.

Observation of structural relaxations in disordered solid media via spectral histories of single impurity molecules

This paper presents the technique and results of the investigation of the structural relaxation in disordered solid media (polyisobutylene, toluene, ortho-dichlorobenzene) at temperatures below the glass transition point via the spectra and fluorescence images of single impurity fluorescent molecules (terrylene, tetra-tert-butylterrylene). Application of the thermal-cycling method has made it possible to significantly extend the temperature range of investigation (from 4.5 K to the glass transition temperature). The changes observed in individual parameters of low-energy elementary excitations of the tunneling and vibrational types due to structural relaxation processes have been studied. It has been found that there is a spatial inhomogeneity in the distribution of the activation temperatures of local relaxation processes.

A tool for alignment of multiple laser beams in pump-probe experiments

Luminescence imaging has been adapted to facilitate alignment and focusing of multiple non-collinear laser beams in pump–probe experiments. The technique has been validated in an experiment on four-wave mixing in a doped polymer placed into a high-pressure sapphire-anvil cell, itself inside an optical cryostat.