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Molecular crystals and liquid crystals science technology. Section A, Molecular crystals and liquid crystals/Molecular crystals and liquid crystals science and technology. Section A, Molecular crystals and liquid crystals

Contributions of The Different Line Broadening Mechanisms in Photon Echoes and Single Molecule Spectra in Amorphous Solids

Yu. G. Vainer, Roman I. Personov, Stephan J. Zilker, D. Haarer

Published Dec 1, 1996• 8 citations
Publisher

Abstract

Experimental data on Photon Echoes (PE) in the system terrylene/poly(isobutylene) in the temperature range 0.4–8K are presented and compared with Single Molecule Spectroscopy (SMS) results. From this comparison we conclude that the linewidth distribution in SMS is caused mainly by a large T 2-dispersion (but not slow spectral diffusion). The temperature line broadening is discussed.

DOI
10.1080/10587259608042730

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Revisiting the combined photon echo and single-molecule studies of low-temperature dynamics in a dye-doped polymer

Mikhail Knyazev, Каримуллин Камиль Равкатович, А. В. Наумов

The photon echo (PE) spectroscopy and single-molecule spectroscopy (SMS) may be combined to give a very powerful tool for comprehensive study of low-temperature dynamics in dye-doped disordered solids (polymers, glasses). At the same time, this type of studies are likely to reveal discrepancies when comparing characteristic times of optical dephasing T2 and single-molecule zero-phonon spectral lines (ZPL) broadening obtained from PE and SMS, correspondingly, for tetra-tert-butylterrylene in polyisobutylene in the temperature range of a few–dozen of Kelvins [see Phys. Status Solidi B 241, 3480 and 3487 (2004)]. Inexplicably, PE-experiments demonstrated T2-times to be much shorter than it is sufficient to cause the corresponding ZPL broadening. Here we experimentally solve this problem and show that at T = 4.5–15 K the incoherent PE gives T2-times which correspond to the narrowest SM ZPL. On the SM-level there is a pronounced additional ZPL-broadening due to spectral diffusion processes which are strongly dependent on the characteristics time of the measurement (tens of nanoseconds for PE and seconds for SMS). There is also a broad distribution of ZPL spectral widths for different SMs due to different local environments, that contribute differently to both the optical dephasing and the spectral diffusion processes, but always in addition to the value of inverse optical dephasing times measured using a PE technique.

physica status solidi (RRL) - Rapid Research Letters•Feb 14, 2017•25 citations

Comparison of photon echo, hole burning, and single molecule spectroscopy data on low-temperature dynamics of organic amorphous solids

Stephan J. Zilker, L. Kador, J. Friebel +3 more

A joint analysis of spectroscopic data obtained at liquid–helium temperatures by three line-narrowing techniques, photon echo (PE), persistent hole burning (HB), and single molecule spectroscopy (SMS), is presented. Two polymer systems, polyisobutylene (PIB) and polymethylmethacrylate (PMMA), doped with tetra-tert-butylterrylene (TBT) were studied via PE and HB techniques and the results are compared with literature data [R. Kettner et al., J. Phys. Chem. 98, 6671 (1994); B. Kozankiewicz et al., J. Chem. Phys. 101, 9377 (1994)] obtained by SMS. Both systems behave quite differently. In TBT/PIB a rather strong influence of a dispersion of the dephasing time T2 was found which plays only a minor role in TBT/PMMA. We have also measured the temperature dependence of T2 for both systems in a broad temperature range (0.4–22 K). Using these data we separated the two different contributions to the optical dephasing — due to an interaction with two-level systems and due to coupling with local low-frequency modes. The data are compared with calculations using a numerical and a semianalytical model in the presence of a large dispersion of the single molecule parameters. Furthermore, we discuss the differences of the linewidths as measured by different experimental methods.

The Journal of Chemical Physics•Oct 22, 1998•31 citations

Incoherent photon echoes with femtosecond time resolution: Principles and applications for studies of low temperature dynamics in amorphous solids

Yu. G. Vainer, Roman I. Personov

The principles of incoherent photon echoes (IPE) are shortly recalled. The results on dynamics in doped organic glasses and polymers (resorufin in d‐ and d6‐ethanol and terrylene in polyethylene) studied by IPE are presented. In all cases the fast dephasing processes are related to coupling with both two‐level systems (TLS) and pseudolocal mode. The nanosecond spectral diffusion (SD) processes has been observed. The IPE‐results are compared with hole‐burning and single molecule spectroscopy (SMS) data.

AIP conference proceedings•Jan 1, 1996•0 citations

Linewidths In Spectra Of Terrylene In Polyethylene Probed By Incoherent Photon Echo. Comparison With Single Molecule Spectroscopy Data

N.V. Gruzdev, Roman I. Personov, Yu. G. Vainer

The concept of the homogeneous spectral linewidth of an impurity center is more complicated in disordered media such as organic glasses and polymers than it is in crystals. In amorphous media the local environments for impurity centers are continuously changing with time. As a result transition frequencies of individual centers diffuse within the inhomogeneous broadened spectral contour, which is called spectral diffusion. When the timescale for spectral diffusion processes is much longer than the dephasing time, it is possible to distinguish homogeneous dephasing from spectral diffusion. On the other hand, when the timescales of spectral diffusion and dephasing processes are comparable these phenomena become indistinguishable.

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Photon Echo and Single Molecule Fluorescence Measurements of Organic Dyes in Thin Polymer Films

Robin Smith

The extraordinarily short optical dephasing time of organic dye molecules in polymer hosts is known to be under 20 fs between 100 and 200 K. Short dephasing times suggest enormously broadened homogeneous linewidths on the order of 10 nm. Direct observation of single dye molecule fluorescence spectra shows a similarly broadened line, giving comparable dephasing times for room temperature measurements. While this single molecule linewidth agrees with that of the bulk sample, it is inaccurate to attribute this broadening to homogeneous mechanisms. Repeated single molecule fluorescence measurements permit determination of the homogeneous nature of this linewidth, as distinct from the inhomogeneous nature of dispersion in bulk samples. Spectral diffusion in single molecule spectra is evidenced by multiple peaks, visible despite broad spectra lines at room temperature. In the particular experiment discussed in this thesis, fluorescence from single organic dye molecules in thin polymethyl methacrylate films was studied with scanning confocal microscopy. Photon antibunching exhibited by the photon-pair correlation function g(2) (τ) at τ = 0 confirms that single molecule emission spectra were obtained.

•Jan 1, 2003•3 citations

Photon echoes in an impurity polymer: New data on the low-temperature processes of phase relaxation and their relationship to the broadening of zero-phonon lines of single molecules

Каримуллин Камиль Равкатович, Mikhail Knyazev, А. В. Наумов

New experimental data on the times of phase relaxation in the amorphous polyisobutylene doped with chromophore molecules of tetra-tert-butylterylene are obtained by the incoherent photon echo method at temperatures of 5, 7, 10, and 15 K. A comparative analysis of the results is performed and data on the widths of zero-phonon spectral lines of single molecules in this impurity system are presented.

Bulletin of the Russian Academy of Sciences Physics•Dec 1, 2014•17 citations
Experimental data on Photon Echoes (PE) in the system terrylene/poly(isobutylene) in the temperature range 0.4–8K are presented and compared with Single Molecule Spectroscopy (SMS) results. From this comparison we conclude that the linewidth distribution in SMS is caused mainly by a large T 2-dispersion (but not slow spectral diffusion). The temperature line broadening is discussed.
The photon echo (PE) spectroscopy and single-molecule spectroscopy (SMS) may be combined to give a very powerful tool for comprehensive study of low-temperature dynamics in dye-doped disordered solids (polymers, glasses). At the same time, this type of studies are likely to reveal discrepancies when comparing characteristic times of optical dephasing T2 and single-molecule zero-phonon spectral lines (ZPL) broadening obtained from PE and SMS, correspondingly, for tetra-tert-butylterrylene in polyisobutylene in the temperature range of a few–dozen of Kelvins [see Phys. Status Solidi B 241, 3480 and 3487 (2004)]. Inexplicably, PE-experiments demonstrated T2-times to be much shorter than it is sufficient to cause the corresponding ZPL broadening. Here we experimentally solve this problem and show that at T = 4.5–15 K the incoherent PE gives T2-times which correspond to the narrowest SM ZPL. On the SM-level there is a pronounced additional ZPL-broadening due to spectral diffusion processes which are strongly dependent on the characteristics time of the measurement (tens of nanoseconds for PE and seconds for SMS). There is also a broad distribution of ZPL spectral widths for different SMs due to different local environments, that contribute differently to both the optical dephasing and the spectral diffusion processes, but always in addition to the value of inverse optical dephasing times measured using a PE technique.
A joint analysis of spectroscopic data obtained at liquid–helium temperatures by three line-narrowing techniques, photon echo (PE), persistent hole burning (HB), and single molecule spectroscopy (SMS), is presented. Two polymer systems, polyisobutylene (PIB) and polymethylmethacrylate (PMMA), doped with tetra-tert-butylterrylene (TBT) were studied via PE and HB techniques and the results are compared with literature data [R. Kettner et al., J. Phys. Chem. 98, 6671 (1994); B. Kozankiewicz et al., J. Chem. Phys. 101, 9377 (1994)] obtained by SMS. Both systems behave quite differently. In TBT/PIB a rather strong influence of a dispersion of the dephasing time T2 was found which plays only a minor role in TBT/PMMA. We have also measured the temperature dependence of T2 for both systems in a broad temperature range (0.4–22 K). Using these data we separated the two different contributions to the optical dephasing — due to an interaction with two-level systems and due to coupling with local low-frequency modes. The data are compared with calculations using a numerical and a semianalytical model in the presence of a large dispersion of the single molecule parameters. Furthermore, we discuss the differences of the linewidths as measured by different experimental methods.
The principles of incoherent photon echoes (IPE) are shortly recalled. The results on dynamics in doped organic glasses and polymers (resorufin in d‐ and d6‐ethanol and terrylene in polyethylene) studied by IPE are presented. In all cases the fast dephasing processes are related to coupling with both two‐level systems (TLS) and pseudolocal mode. The nanosecond spectral diffusion (SD) processes has been observed. The IPE‐results are compared with hole‐burning and single molecule spectroscopy (SMS) data.
The concept of the homogeneous spectral linewidth of an impurity center is more complicated in disordered media such as organic glasses and polymers than it is in crystals. In amorphous media the local environments for impurity centers are continuously changing with time. As a result transition frequencies of individual centers diffuse within the inhomogeneous broadened spectral contour, which is called spectral diffusion. When the timescale for spectral diffusion processes is much longer than the dephasing time, it is possible to distinguish homogeneous dephasing from spectral diffusion. On the other hand, when the timescales of spectral diffusion and dephasing processes are comparable these phenomena become indistinguishable.
The extraordinarily short optical dephasing time of organic dye molecules in polymer hosts is known to be under 20 fs between 100 and 200 K. Short dephasing times suggest enormously broadened homogeneous linewidths on the order of 10 nm. Direct observation of single dye molecule fluorescence spectra shows a similarly broadened line, giving comparable dephasing times for room temperature measurements. While this single molecule linewidth agrees with that of the bulk sample, it is inaccurate to attribute this broadening to homogeneous mechanisms. Repeated single molecule fluorescence measurements permit determination of the homogeneous nature of this linewidth, as distinct from the inhomogeneous nature of dispersion in bulk samples. Spectral diffusion in single molecule spectra is evidenced by multiple peaks, visible despite broad spectra lines at room temperature. In the particular experiment discussed in this thesis, fluorescence from single organic dye molecules in thin polymethyl methacrylate films was studied with scanning confocal microscopy. Photon antibunching exhibited by the photon-pair correlation function g(2) (τ) at τ = 0 confirms that single molecule emission spectra were obtained.