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The Journal of Chemical Physics

Nonlinear line narrowing of excited state resonances in perylene doped poly(methylmethacrylate) using multiply enhanced nonparametric spectroscopy

Gregory B. Hurst, John Curtis Wright

Published Aug 1, 1991• 19 citations
Publisher

Abstract

Line narrowing of perylene vibronic transitions in poly(methylmethacrylate) (PMMA) samples has been demonstrated using multiply enhanced nonparametric spectroscopy. Three lasers are used to generate a four wave mixing signal that is resonantly enhanced by three simultaneous perylene resonances involving a vibrational state, a vibrationless excited electronic state, and a vibronic state of the excited electronic state. There is a correlation between the position of the electronic and vibronic states within the inhomogeneously broadened absorption spectrum. The correlation can be used to achieve line narrowing by fixing one of the resonances to a subset of perylene sites within the inhomogeneous profile so the other resonance of those sites will be selectively enhanced. The position of the line narrowed vibronic peaks depends upon the electronic detuning from the center of the inhomogeneously broadened absorption band as different sites within the band are probed. Excited state coherent processes involving resonance with higher singlet states are shown to be unimportant from the detuning dependence on a simultaneous vibrational enhancement.

DOI
10.1063/1.461063

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Line narrowing of perylene vibronic transitions in poly(methylmethacrylate) (PMMA) samples has been demonstrated using multiply enhanced nonparametric spectroscopy. Three lasers are used to generate a four wave mixing signal that is resonantly enhanced by three simultaneous perylene resonances involving a vibrational state, a vibrationless excited electronic state, and a vibronic state of the excited electronic state. There is a correlation between the position of the electronic and vibronic states within the inhomogeneously broadened absorption spectrum. The correlation can be used to achieve line narrowing by fixing one of the resonances to a subset of perylene sites within the inhomogeneous profile so the other resonance of those sites will be selectively enhanced. The position of the line narrowed vibronic peaks depends upon the electronic detuning from the center of the inhomogeneously broadened absorption band as different sites within the band are probed. Excited state coherent processes involving resonance with higher singlet states are shown to be unimportant from the detuning dependence on a simultaneous vibrational enhancement.
We explain the utility of third-order nonlinear susceptibility, χ (3) (ω 2 ; ±ω 1 , ∓ω1{\mp}\omega_{1}∓ω1​, ω 2 ), for the observation of resonances with homogeneous widths from inhomogeneously broadened distributions in three-level systems related to Raman or two-photon allowed electronic transitions. The line narrowing and high resolution capabilities are demonstrated theoretically using a model for inhomogeneous distributions of transitions in which we regard an absorption spectrum as the composition of some inhomogeneously broadened substructures. The experimental methods to separate a signal having frequency ω 2 from ingoing beam at the same frequency are outlined.
The study of optical relaxation processes in solids at low temperature has progressed tremendously in the last 20 years due to the development of coherent optical techniques. The latter would not have been possible without the advent of narrow-band tunable lasers, on the one hand, and lasers with very short pulses (picoseconds, femtosecoods) on the other hand. Such coherent techniques are necessary because spectral line shapes of solids doped with guest molecules are seldom determined by dynamical interactions but principally by strain or structural disorder. This gives rise to inhomogeneous broadening, rlOh, which in crystalline hosts at low temperature varies between ' 0.1 and 10 cm -I, whereas in glasses it may amount to � 100-500 em-I. One of the techniques to achieve narrowing of spectral lines is site­ selection spectroscopy (1-3). A sub-ensemble of molecules within thc inhomogeneously broadened absorption band is selectively excited by mcans of a narrow-band laser, and the fluorescence or phosphoresccnce signal is detected with a high-resolution monochromator and/or a Fabry­ Perot interferometer. Fluorescence line-narrowing ( I) is a special case of this technique (for a review see 3). The intrinsic or homogeneous spectral linewidth, r hom, which yields information on the relaxation processes of the excited state, is given by the effective optical dephasing time, T2:
Recent research has expanded the capabilities of four-wave mixing by providing it with component selectivity, site selectivity, and mode selectivity. The selectivity is achieved by taking advantage of the three resonance enhancements that occur in a four-wave mixing process. New spectral scanning strategies allow one to scan a single resonance while maintaining the other two resonances at constant values. The constant resonances can be used to select a specific component, a specific site within an inhomogeneously broadened envelope of a component, and/or a specific vibrational or vibronic mode of that site. The scanned resonance will then contain enhanced features corresponding to the particular component, site, and/or mode that was chosen by the constant resonances. These component and site selective capabilities of the four-wave mixing complement the single vibronic level fluorescence methods. The relative transition intensities from a specific component or site reflect the mode coupling between the vibrational and vibronic modes. Since the four-wave mixing is fully resonant in these experiments, saturation effects play a dominant role and cannot be ignored. This review presents a complete discussion of the theoretical and experimental factors that control the fully resonant four-wave mixing. It shows examples of the component selectivity and the line narrowing capabilities. It also provides examples of how mode selection can identify mode coupling through the relative intensities of different vibrational features.
Four-wave mixing processes with double and triple resonances are discussed in detail. Explicit expressions for the resonant nonlinear susceptibilities of various cases are derived. It is shown that in some cases, four-wave mixing can yield a spectrum with reduced inhomogeneous broadening. Possible applications of multiresonant four-wave mixing as a spectroscopic technique are considered. They include high-resolution spectroscopy, deduction of transition matrix elements, study of transitions between excited states, measurement of longitudinal relaxation times, distinction between resonant Raman scattering and resonant fluorescence, etc. Selective polarization arrangement allows us to suppress the nonresonant background, separately measure the real and imaginary parts of the resonant nonlinear susceptibility, minimize the effects of absorption and laser intensity fluctuations, and greatly enhance the signal-to-noise ratio.
Abstract Inhomogeneous broadening is often considered a nuisance in solid state spectroscopy, and the usual treatment of it is phenomenological. In fact, the inhomogeneous broadening of absorption spectra, coupled with a microscopic theory, can provide one with interesting information about the nature of disorder in different systems. More sophisticated experiments can provide more detailed information about disorder by probing certain correlations between energy levels. For example, flourescence line narrowing spectra of isolated impurities involve correlations among three different vibronic levels. Pressure effects on hole burning spectra probe correlations of impurity transition energies before and after the pressure change. For interacting impurity systems, photon echo experiments involve transition energy correlations between different impurities. Efforts to understand these effects within a microscopic framework are discussed.
The stationary second-order spectrum of the resonance-fluorescence light from a vibronic system is studied in a nonperturbative manner. In the model used the potential energy surfaces for the vibrational motion in the electronic ground state and in the excited state are assumed to be displaced and distorted relative to each other. The calculations are performed for the case when the frequency of the driving laser field is tuned to the vibrationless electronic transition. In particular, in the high-driving-field limit the vibrationless transition exhibits a triplet structure, the sidebands being narrower and higher in comparison with the well-known two-level case. The Raman lines are shifted and split into doublets, the linewidths being determined by the electronic as well as the vibrational relaxation rates.