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Journal of the Optical Society of America B

Dispersive kinetics of nonphotochemical hole burning and spontaneous hole filling: Cresyl Violet in polyvinyl films

Luchuan Shu, Gerald J. Small

Published May 1, 1992• 30 citations
Publisher

Abstract

The dispersive kinetics of nonphotochemical burning and spontaneous filling of the zero-phonon hole of Cresyl Violet in polyvinyl alcohol at 1.6 K are analyzed in terms of the standard external two-level system (TLSezt) model for probe–glass systems and a distribution function for the tunnel frequency derived from a normal distribution function for the tunnel parameter λ. Average values for the relaxation rates for burning and filling are determined. It is shown that the dominant mechanism for filling is not global spectral diffusion but rather antihole reversion. A high degree of positive correlation between the rates of burning and filling associated with the TLSext is found. A new methodology that permits a more physically reasonable interpretation of spontaneous hole-filling kinetics is described. It is based on the hypothesis that only a fraction of burned sites, on reversion to the ground state, yield sites with resonance frequencies that lie within the hole profile.

DOI
10.1364/josab.9.000733

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The dispersive kinetics of nonphotochemical burning and spontaneous filling of the zero-phonon hole of Cresyl Violet in polyvinyl alcohol at 1.6 K are analyzed in terms of the standard external two-level system (TLSezt) model for probe–glass systems and a distribution function for the tunnel frequency derived from a normal distribution function for the tunnel parameter λ. Average values for the relaxation rates for burning and filling are determined. It is shown that the dominant mechanism for filling is not global spectral diffusion but rather antihole reversion. A high degree of positive correlation between the rates of burning and filling associated with the TLSext is found. A new methodology that permits a more physically reasonable interpretation of spontaneous hole-filling kinetics is described. It is based on the hypothesis that only a fraction of burned sites, on reversion to the ground state, yield sites with resonance frequencies that lie within the hole profile.
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.
The results of nonphotochemical hole burning (NPHB) and laser induced hole filling (LIHF) experiments are reported for several impurities intentionally doped into thin polymer films. The polymer films provide an amorphous environment for the dopants which can be easily and reproducibly prepared at room temperature, and they are convenient in handling since they are solids at ordinary temperatures. Thus, polymer films have several advantages over the various low temperature glasses which have been used previously for NPHB studies. The systems studied include the polymers poly(vinyl alcohol) and poly(acrylic acid) doped with various organic ionic dyes (cresyl violet, rhodamine 560 and 640, nile blue, and oxazine 720 and 725, all of which are used as the active gain medium in dye lasers) as well as the rare earth ions Pr('3+) and Nd('3+). Additionally, polystyrene was used as the amorphous host in NPHB and LIHF studies of chlorophyll a, chlorophyll b and self-aggregated dimers of chlorophyll a;The NPHB of the ionic dyes is efficient, and the spectra exhibit extensive intramolecular vibronic satellite holes which provide accurate S(,1) vibronic frequencies for the dopant. The homogeneous linewidths of the impurity S(,0) (--->) S(,1) transitions inferred from measured hole widths yields dephasing rates which are one to two orders of magnitude faster than observed in crystals and "hard" inorganic glasses (silica e.g.), and is taken as evidence for rapid pure dephasing processes occurring in the polymer systems even at 1.8 K. The LIHF of these systems is also efficient and shows a pronounced change in efficiency when the relative magnitudes of the laser frequencies for the first and second irradiations is reversed. Also, the efficiency of LIHF is insensitive to the amount of radiation absorbed by the dopant, and hence shows little change as the secondary burn frequency is moved relative to the primary frequency (except as noted above). This same LIHF behavior was observed in all the systems reported herein and may have profound implications as to the structure of glassy media;The chlorophyll systems also show efficient NPHB but no intramolecular vibronic holes are observed. These systems also show evidence of rapid pure dephasing processes even at 1.8 K. The results obtained for the monomer chlorophyll NPHB are used to help interpret the results obtained for the self-aggregated dimers which, in turn, were obtained to help in the interpretation of planned future experiments on chlorophylls in in vivo environments;Finally, a brief review of relevant NPHB research and the various theories used to describe the hole burning process is presented.
With high-efficiency fluorescence excitation techniques optical spectra of single impurity molecules of perylene in a polyethylene matrix can be obtained at 1.5 K. Analysis of such spectra shows a variety of spectral diffusion effects, including fast (<2 s) resonance frequency changes on the 1–100-MHz scale, which lead to a range of apparent linewidths, as well as discontinuous jumps in the resonance frequency of 10–1000 MHz on a longer time scale. In addition, light-induced changes in the resonance frequency of a single molecule (persistent spectral hole burning) have been conclusively observed by showing that the burning time decreases with increased laser power. Surprisingly, hole-burned single molecules often spontaneously return to the original frequency in 1–100 s. Measurements of the burning time for a large number of hole-burning events for the same single molecule yield an exponential burn-time distribution, which is the first direct measurement to our knowledge of the stochastic kinetics of a single molecule. Analysis of the signal-to-noise function appropriate to these experiments gives the conditions under which other systems may permit single-molecule detection: strong absorption, high fluorescence yield, weak bottlenecks in the optical pumping process, and low hole-burning quantum efficiency.
Ultrafast homogeneous transverse relaxation time (dephasing time) T2 of Cresyl Fast Violet in cellulose has been measured in the S0 ↔ S1 transition by photon echoes with temporally incoherent nanosecond laser pulses. At 10 K, T2 was 0.7 psec when the sample was excited 6250 Å near the long-wavelength edge of the absorption band, but it was several tens of femtoseconds at 5940 Å. The fact that T2 is shorter at shorter wavelengths can attributed to the intramolecular relaxation of Cresyl Fast Violet molecules. T2 was measured also at 80 and 300 K. At 10 K persistent nonphotochemical holes (PNPH’s) were observed, and the relations between T2 and the shapes of the PNPH’s have been considered.
The change in the profile of a spectral hole can be used to detect tunneling processes in glassy matrices as well as light-induced changes of molecular configurations. The broadening of photochemical holes as well as hole-filling processes are very sensitive probes for molecular rearrangements arround the embedded dye molecules /1/. Light-induced spectral diffusion in polymeric systems is highly selective with respect to the optical excitation of vibrational modes of the surrounding molecular groups.