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Proceedings of SPIE, the International Society for Optical Engineering/Proceedings of SPIE

Laser Spectroscopy Of Electronic Resonances: An Electro-Optic Technique For Probing Coherent And Incoherent Decay Processes

Ahmed H. Zewail

Published Dec 30, 1976• 4 citations
Publisher

Abstract

A new technique is presented for measuring the incoherent resonance decay (IRD) and the coherent optical ringing of selectively (5 MHz) prepared electronic states. The method utilizes electro-optic switching of a single laser mode that is on or off resonance with respect to the homogeneous molecular packets in the excited ensemble. The technique was applied to a variety of systems (gases at low pressures, gases at relatively high pressures, and solids at low temperatures) to give information about their phase memory (optical T2 processes), radiative and radiationless decay (optical T1 processes), and to measure directly their optical transition moment between the ground state and the prepared electronic state. The theory of coherent and incoherent states is also given.

DOI
10.1117/12.954871

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A new technique is presented for measuring the incoherent resonance decay (IRD) and the coherent optical ringing of selectively (5 MHz) prepared electronic states. The method utilizes electro-optic switching of a single laser mode that is on or off resonance with respect to the homogeneous molecular packets in the excited ensemble. The technique was applied to a variety of systems (gases at low pressures, gases at relatively high pressures, and solids at low temperatures) to give information about their phase memory (optical T2 processes), radiative and radiationless decay (optical T1 processes), and to measure directly their optical transition moment between the ground state and the prepared electronic state. The theory of coherent and incoherent states is also given.
A novel spectroscopic tool is presented for measuring the incoherent resonance decay (IRD) of selectively (6 MHz) prepared electronic states. The method utilizes electro-optic switching of a single laser mode that is on or off resonance with respect to the homogeneous molecular packets in the excited ensemble. The technique is applied to a variety of systems: gases at low and high pressures, molecular beams, and solids at low temperatures. The coherent transient of solids observed in the forward direction of the laser gives the phase memory (optical T2 processes) while the IRD measures directly the radiative and radiationless decay (optical T1 processes), and the optical transition moment between the ground state and the prepared electronic state. The theory of coherent and incoherent states is also given, and related to the different aspects of time-resolved spectroscopy of molecular beams and solids.
I. A new technique utilizing the electro-optic frequency switching of a single mode ( 6 Mhz) dye laser was used to observe free induction decay and optical nutation in iodine gas and optical nutation in an organic mixed crystal (pentacene in p-terphenyl) at low temperature. A new technique, incoherent resonance decay (IRO) was also developed. These experiments allow one to determine T_1 and T_2, the longitudinal and transverse relaxation times of the excited ensemble, in analogy with magnetic resonance. For I_2(g) at O∙C; T_l = 2.3 x 10^(-7) sec, T_2 ≃ 1 x 10^(-7) sec. These techniques are limited to a time scale > 10 nsec. II. The construction and characterization of cw, mode-locked dye laser capable of putting out a continuous train of reproducible sub-picosecond pulses is described. Experiments utilizing this laser for the measurement of picosecond coherent transients and time resolved absorption spectroscopy are proposed.
Traditionally, the phenomenon of optical coherence has been observed by detecting coherent transients (i.e., optical nutation, FID, photon echoes) propagating along the laser beam following passage through an absorbing medium. Recently, we have demonstrated that detection of the incoherent (spontaneous) emission from selectively prepared states provides the optical coherence of the ensemble. Our observation of the nutation and the photon echo at right angles to the exciting beam gives directly optical T_1, T_2, and the moment of the laser excited transition. This technique is simple and not susceptible to some of the problems inherent in coherent absorption experiments. Details about this laser technique will be presented. We will also discuss the different dynamical information one obtains about excited states in gases, molecular beams and solids.
Recently we have reported[1] on the measurements of electronic dephasing (T_2) and radiationless decay (T_1) in molecules using emission spectroscopy as a probe for the detection of the photon echo. This right-angle photon echo utilizes a single mode of a narrow-band (~MHz) cw dye laser and an intracavity electro-optical (EO) element that modulates the frequency of the laser.[2] Applying voltage pulses into the EO crystal switches the laser frequency from ω_0 (the peak frequency of the transition resonance) into another frequency ω. This switching procedure introduced by Brewer et al. for the observation of transients in the forward direction of the laser allows one to observe coherent transients in gases,[1,2] solids[3-5] and molecular beams.[6] Typically, the dispersion of the nonlinear EO crystal (e.g., AD*P) gives a 60 MHz frequency shift within the inhomogeneous resonance of the optical transition (width ~GHz or larger). Therefore, to switch the laser frequency further, one must use high-voltage signals that are usually hard to obtain especially for multiple-pulse experiments. Secondly, there is a limit on the frequency shift which is conditioned by the mode spacing of the cavity. Thirdly, because the laser is switched into a new group of molecules some complications may arise in interpreting the transient spectra especially in large molecules. This is because in large molecules the density of excited states is high and thus the buildup of transients of w molecules (which could be complex) will be superimposed on the decay of ω_0 molecules. Finally, off-resonance effects (e.g., beats) between the molecules at frequency ω and ω_0 cannot be avoided.
This chapter is devoted to the description of the main methods employed in the investigation of optical transient processes in gas media and the apparatus used in these studies. Recently, a new direction of laser spectroscopy has appeared. This direction is based on several methods of extracting the information concerning a resonant medium, including: a ) analysis of decay curves for the intensities of optical coherent responses within certain time intervals; b) analysis of temperature lowering, i.e., the dependencies of the intensities of coherent responses on the temperature of a gas medium under study; c) investigation of the modulated structures of optical coherent responses related to the hyperfine coupling of unpaired electrons with nuclei of molecules or atoms in the gas (modulation coherent spectroscopy), including the regime of double resonances; d) polarization coherent spectroscopy associated with the identification of the type of the energy transition being studied and the determination of characteristics of this transition from the polarization properties of optical coherent responses; e) the method of optical “coherent averaging,” which is closely related to a multipulse excitation of gas particles and the regime of double resonances; and ƒ) the method of angular spectroscopy, which is based on the spatial features of the generation of optical coherent responses and superradiance.