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The Journal of Chemical Physics

Theory of transient hole-burning spectrum for molecules in solution

Shuichi Kinoshita

Published Nov 1, 1989• 60 citations
Publisher

Abstract

Theory based on a configuration coordinate model is presented to clarify solute–solvent relaxation effect on the line shape of a time-resolved hole-burning spectrum. The time-resolved hole-burning spectrum is affected by both a hole created in a ground-state population and an excess excited-state population. The solute–solvent relaxation causes thermalization in both populations and then the shift and broadening of the spectrum is expected observable. The line shapes of three typical cases are mainly considered: (1) The excited state is assumed to have an infinitely long lifetime; (2) the excited state has a finite lifetime, the population being assumed to relax toward an electronic state other than the ground state, and (3) the population created in the excited state relaxes to the ground state, where a hole-filling effect is taken into account. Results obtained by numerical calculations show that a time evolution of the ground-state hole is clearly observed when the low-energy tail of the absorption band is excited under the condition that the population decay to the other electronic state is very fast. Further, it is predicted that the hole-filling effect causes a considerable deformation of the spectral shape when the solvent relaxation rate is comparable to the excited-state population decay rate.

DOI
10.1063/1.457617

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The Journal of Chemical Physics•Jun 15, 1991•21 citations
Theory based on a configuration coordinate model is presented to clarify solute–solvent relaxation effect on the line shape of a time-resolved hole-burning spectrum. The time-resolved hole-burning spectrum is affected by both a hole created in a ground-state population and an excess excited-state population. The solute–solvent relaxation causes thermalization in both populations and then the shift and broadening of the spectrum is expected observable. The line shapes of three typical cases are mainly considered: (1) The excited state is assumed to have an infinitely long lifetime; (2) the excited state has a finite lifetime, the population being assumed to relax toward an electronic state other than the ground state, and (3) the population created in the excited state relaxes to the ground state, where a hole-filling effect is taken into account. Results obtained by numerical calculations show that a time evolution of the ground-state hole is clearly observed when the low-energy tail of the absorption band is excited under the condition that the population decay to the other electronic state is very fast. Further, it is predicted that the hole-filling effect causes a considerable deformation of the spectral shape when the solvent relaxation rate is comparable to the excited-state population decay rate.
A number of limitations to hole burning in the liquid phase are identified. As spectral diffusion becomes more rapid, a point is reached where the narrowest hole width no longer measures the homogeneous linewidth. Spectral congestion of the solute is also shown to limit the fastest detectable spectral diffusion rate. An optimal pulse length is found which allows observation of the most rapid spectral diffusion. In addition, the coherence effect observed when the pulses overlap is shown to have resonances at both the excited and ground state vibrational spacings. The coherence effect greatly resembles the hole burning spectrum, but contains no dynamical information. Because of these limitations, hole burning may not be observed even when the homogeneous spectrum is well resolved and spectral diffusion is slow. Experimental confirmation is found in the hole burning spectrum of iodine in hexane, which shows no hole burning despite having a narrow homogeneous linewidth.
Abstract A two‐step spectral hole burning (SHB) is considered, where the selective excitation of the first step is fixed by a photochemical transformation through the second excitation step. It is shown that in a three‐level system excited by two consecutive pulses, the kinetics of the forming spectral hole differs essentially from the one on stationary irradiation. In the case of a short second pulse the shape of the hole in the inhomogeneous distribution function (IDF) of the purely electronic line frequency Ω01 is dependent on the time interval T between the first and second excitation steps and under certain conditions a hole can be obtained which is narrower than in the one‐step SHB with monochromatic light. It is considered how the hole in IDF is manifested in the absorption and two‐step pulse excitation spectra. It is shown that the hole in the absorption spectrum may be narrower than 2γ1 and in the two‐step pulse excitation, −γ1 (γ1 is the energy relaxation constant of the first excited level).
A theory is presented for the effect of cross relaxation (CR) on the saturation with driving-signal intensity of the steady-state gain of a laser amplifier with an inhomogeneously broadened linewidth. The condition of steady-state gain results when the amplifier excitation level W and the driving-signal intensity are constant for about 3τ or longer, where τ is the fluorescence lifetime of the upper laser level. The driving signal is derived from an oscillator operated in the normal mode and which does not saturate the amplifier inversion density over times short compared with τ. We assume that CR, at a rate F, restores to thermal equilibrium any distortion of the spectral inversion density caused by the driving signal. Formulas are derived for steady-state gain saturation with arbitrary F for two cases: the spectral width of the driving signal is (1) narrow and (2) broad relative to the ionic or homogeneous line. The ionic linewidth Δvi is assumed to be much less than the inhomogeneous linewidth Δva and refers to the minimum frequency interval for which infinitely fast CR is operative. The theory also yields the CR coefficients f=(Δvi/Δva) [F/(τ−1+W)] for the narrow-band case and f*=(Δvs/Δva) [F/(τ−1+W)] for the broadband case, where Δvs is the driving-signal bandwidth. These coefficients significantly parametrize the CR effect: for f, f*>1, hole-burning is not severe, whereas for f, f*<1, considerable hole-burning takes place and the gain saturates faster. Finally, the theory is applied to experimental results obtained for Nd3+:glass broadband and narrow-band amplification; an approximate lower bound of 4×105 sec−1 is determined for F.
A model calculation is presented that describes the features of spectral-hole burning measurements performed under conditions of femtosecond transient excitation and probing. Pump-induced changes in the spectrum of probe transmittance arise not only from changes in level population (hole burning), but also from the presence of pump polarization during the probe, and from perturbations of the decay of the probe polarization. These latter effects give rise to oscillating differential transmittance spectra when the (shorter) probe pulse arrives prior to the peak of the pump noise. Only when the probe pulse follows the bulk of the pump pulse does the level population effect dominate the spectrum, so that one can observe dynamic hole-burning effects without distortion.>
We calculate the signal in a time-resolved, coherent light scattering experiment on a dilute solution of a nonpolar solute dissolved in a nonpolar solvent. We model the solute and solvent molecules as electronic two level systems, and assume that only the solute interacts with radiation. The electronic degree of freedom is treated perturbatively within the Born–Oppenheimer approximation. The nuclear degrees of freedom are treated classically, and their effects are modeled by a molecular dynamics simulation. We assume the electronic absorption spectrum is dominated by inhomogeneous broadening. The validity of this assumption for our model is verified through the calculation of the absorption line shape with and without the inhomogeneous broadening assumption. A quantitative measure of the homogeneous dephasing time is obtained from a calculation of the photon echo signal for our model. The time dependence of the light scattering signal is shown to reflect both dynamics of the fluid in its electronic ground state and in its electronic excited state. We analyze the relative importance of contributions to the signal from these two types of dynamics as a function of experimental time scale and laser frequency.