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Journal of the Optical Society of America B

Resonant inhomogeneous molecular absorption of ultrashort laser pulses: role of the pulse spectrum

Pritish Mukherjee, Hoi Sing Kwok

Published Mar 1, 1993• 1 citation
Publisher

Abstract

A model molecular system composed of an inhomogeneous distribution of homogeneous wave packets is presented in analogy with gain saturation in atomic systems. The numerically computed optical free-induction-decay pulse spectrum (as a representative picosecond-pulsed laser system) and other idealized pulse spectra are used as inputs to the molecular system to probe its absorption characteristics in the inhomogeneous limit. Various aspects of pulse spectral structure and their relative significance to the observed nonlinearity of the numerically computed 1/σ2-versus-I plot is discussed in detail. The relevance of such behavior in interpreting experimental data is also indicated.

DOI
10.1364/josab.10.000425

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A model molecular system composed of an inhomogeneous distribution of homogeneous wave packets is presented in analogy with gain saturation in atomic systems. The numerically computed optical free-induction-decay pulse spectrum (as a representative picosecond-pulsed laser system) and other idealized pulse spectra are used as inputs to the molecular system to probe its absorption characteristics in the inhomogeneous limit. Various aspects of pulse spectral structure and their relative significance to the observed nonlinearity of the numerically computed 1/σ2-versus-I plot is discussed in detail. The relevance of such behavior in interpreting experimental data is also indicated.
Because of inevitable size distribution, shape variations, different concentration of impurities and defects, and fluctuations of local environment and charge distribution, every ensemble of nanocrystals dispersed in some solid or liquid medium possesses inhomogeneously broadened absorption and emission spectra. Therefore, a number of properties inherent in molecular and atomic inhomogeneously broadened spectra can be a priori foreseen for nanocrystals. These include spectral hole-burning, fluorescence line narrowing under selective excitation, and decay time distribution. At the same time, spectrally selective techniques developed for inhomogeneously broadened molecular and atomic structures have been successfully applied to nanocrystals providing evaluation of individual parameters smeared as a result of inhomogeneous broadening. This chapter gives a brief overview of specific phenomena inherent in all spectrally inhomogeneous media and a survey of the relevant experimental techniques including nonlinear pump-and-probe spectroscopy, fluorescence excitation spectroscopy, and single molecule spectroscopy. Population-induced optical nonlinearity and spectral hole-burning Every real system consisting of particles with discrete energy levels exhibits absorption saturation under intense optical excitation. The only example of a nonsaturable system is an ensemble of ideal harmonic oscillators that possess an infinite number of equally spaced energy levels, optical transitions allowed only for a couple of neighboring levels, and the probability of optical transitions being proportional to the level number (Stepanov and Gribkovskii 1963).
Most chirped-pulse experiments refer to a theoretical study from McGurk, Schmalz, and Flygare [J. Chem. Phys. 60, 4181 (1974)] which is well tailored to interpret the signals obtained with very fast chirped pulses, but is not sufficient to account for the signals in the case of slower chirped pulses used in spectroscopy to increase the signal-to-noise ratio. A theoretical study of the polarization of molecules subjected to a chirped pulse in a cell, uniform supersonic flow, or molecular beam is presented. Three degrees of approximation for the polarization are introduced and are compared with the numerical solution of the optical Bloch equations. These expressions enter the analytic expression of the free-induction-decay signal which is validated against experimental data on the rotational emission spectra of OCS molecules. A relation among the pulse duration, the line position in the chirped pulse, and the signal amplitude is proposed in the thermalized case. It assists in the optimization of the chirped-pulse parameters and in the estimation of the error associated with the line intensity.
We theoretically and experimentally study absorption of picosecond laser pulses in materials described by a four-level system that exhibit reverse saturable absorption (RSA). Using an approximate solution to the rate equations, we derive, analyze, and verify, numerically and experimentally, a single dynamical equation for the spatial evolution of the pulse fluence that includes both the rate equations and the propagation equation. This analytical approach considerably simplifies the study of optical limiting with picosecond pulses and helps to predict the behavior of the nonlinear transmittance, the level of output signal clamping, and a possible turnover from RSA to saturable absorption that restricts the performance of optical limiters based on RSA. The results obtained can also be used to characterize RSA materials by the pump–probe technique.
Polarization and Rayleigh type optical mixing spectra of a homogeneously and inhomogeneously broadened two-level system are calculated. We show that the nonlinear signal has contributions from the population pulsation and saturation effect. In the homogeneous system these effects can induce an asymmetric spectrum when the probe frequency is different from the resonant value. In the inhomogeneous system the spectral response is always symmetric independent of the probe frequency value. Line saturation and dynamic stark splitting are substantially reduced in the inhomogeneous case. The mentioned differences can be used to identify the type of broadening of a given spectral line.
The propagation of ultrashort few-cycle laser pulses through a quantum nonlinear medium with resonant properties is studied using the method of slowly varying amplitudes with allowance for dispersion effects. A self-consistent system of nonlinear wave equation for the evolution of laser field and the nonstationary Schrödinger equation that determines the material polarization response is numerically solved. Specific features of the propagation of laser pulse caused by a relatively large spectral width and the nonadiabatic character of the laser pulse are established. The rise of the slowly dumping polarization at the eigenfrequency of the medium and the consequent stretching of the laser pulse are observed. The role of the resonant absorption of the laser energy in the medium is analyzed. The nonlinear spectral broadening is demonstrated for the laser pulse propagating through the medium.