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The Journal of Chemical Physics

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, Yu. G. Vainer, M. A. Kol’chenko, Roman I. Personov

Published Oct 22, 1998• 31 citations
Publisher

Abstract

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.

DOI
10.1063/1.477324

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EPJ Web of Conferences•Jan 1, 2018•0 citations
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 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.
We report pressure (0–28 kbar) and temperature (1.1–4.3 K) dependent photon echo results for tetra-tert-butyl-terrylene (TBT) in a polyisobutylene (PIB) host. Increased pressure is found to increase the homogeneous dephasing rate over the temperature range of this study, in contrast to pressure dependent hole burning results reported for other polymer systems at somewhat higher temperatures (⩾4.2 K). A relatively small pressure increase (0 to 9 kbar) resulted in a change in the temperature dependence of the dephasing characterized by a lowering of the temperature power law exponent from ∼1.3 to ∼0.9. Further pressure increase above 9 kbar was characterized by an additional increase in the homogeneous dephasing rate without further change in the temperature exponent. The results are compared to high pressure photon echo studies of other polymer systems, and discussed in terms of the TLS (two-level-systems) model.
Picosecond photon echo experiments on pentacene in polymethylmethacrylate (PMMA) show that the homogeneous width exhibits a T1.3 temperature dependence. This behavior is ascribed to coupling of the pentacene transition to randomly distributed low-frequency excitations in the amorphous host. A calculation of the resulting homogeneous width is presented which uses optical Redfield theory as a starting point. From the results of this calculation we conclude that the coupling between the pentacene molecule and the host low frequency excitations is of static dipolar nature and that the density of states of these excitations varies as ω0.3. Results of nonphotochemical hole-burning experiments on the same system are also reported. Comparison of these results with the ones obtained by the photon echo method indicates, that in the hole-burning experiments, the hole width and its temperature-induced broadening are dominated by spectral diffusion.