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Physical Review A

Stark-induced phase modulation in coherent Raman spectroscopy

Hans Moosmüller, D A Krueger, C. Y. She

Published Dec 1, 1988• 3 citations
Publisher

Abstract

The phase of molecular motion is modulated by the optical Stark effect due to high-intensity laser beams. This is shown to lead to modulation in coherent Raman spectra. The spectral modulation is more pronounced in stimulated Raman spectroscopy than in four-wave-mixing Raman spectroscopy. Increased damping reduces the phase modulation leading to the commonly known spectra.

DOI
10.1103/physreva.38.6210

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The phase of molecular motion is modulated by the optical Stark effect due to high-intensity laser beams. This is shown to lead to modulation in coherent Raman spectra. The spectral modulation is more pronounced in stimulated Raman spectroscopy than in four-wave-mixing Raman spectroscopy. Increased damping reduces the phase modulation leading to the commonly known spectra.
The signal generation in four-wave-mixing Raman spectroscopy and stimulated Raman spectroscopy is theoretically investigated for focused Gaussian beams. Signal strength as a function of interaction length and total signal generation are calculated for both types of coherent Raman spectroscopies. We further discuss the application of our theory to spatially inhomogeneous broadening, especially optical Stark broadening, induced by one of the laser beams. Intensity and phase contours of a Gaussian beam are also presented to enhance the understanding of intensity-dependent interactions.
The four-wave mixing produced with two ultrashort phase-locked !-3! laser pulses propagating coherently in a two-level system in the infrared spectral region is shown to depend on the pulses relative phase. The Maxwell-Bloch equations are solved beyond the rotating-wave approximation to account for field frequencies which are largely detuned from the atomic resonance. The relative phase dominating the efficiency of the coupling to the 5! anti-Stokes Raman component is determined by sign of the total ac Stark shift induced in the system, in such a way that the phase influence disappears precisely where the ac Stark effect due to both pulses is compensated. This fundamental quantum interference effect can be the basis for nonlinear ultrafast optical spectroscopy techniques. Phenomena arising from the coherent control of nonlinear interactions are of importance in fields as diverse as optoelectronics and materials research, in high harmonic generation, in photoionization or molecular dissociation, and in biological applications such as spectroscopy and imaging, among others [1, 2, 3, 4, 5, 6, 7]. Optical quantum coherent control is based on the fact that the phases of interfering transition amplitudes in light-matter interactions can be controlled through the optical phase of coherent light sources that drive the interaction, in such a way that the transition rates to final states and the dynamics at various stages of the process can be modified [1]. In a recent paper [8], a theoretical investigation on the quantum coherent control of the optical transient four-wave mixing of two intense phase-locked femtosecond laser pulses of central angular frequencies ω and 3ω propagating in a two-level atom (TLA) was reported. It was shown how the nonlinear (χ (3) ) coupling to the antiStokes Raman field at frequency 5ω depends critically on the initial relative phase φ of the propagating pulses. In Ref. [8], the study was centered to intense pulses in the visible and ultraviolet spectral regions, with frequencies at resonance or lower than the atomic transition. The phenomena observed in [8], however, can be scaled to various laser and material parameters. In the infrared spectral range, for instance, experiments on ultrafast molecular dynamics are frequently performed by help of twocolor pump probe nonlinear spectroscopy techniques. In this type of studies, due to the high intensities inherent to ultrashort (subpicosecond) pulses, nonlinear effects such as stimulated Raman processes may become important and are often utilized as a complementary tool to gain information [9]. In this Letter, we address the conditions for quantum coherent control of transient four-wave mixing interactions with two phase-locked ω-3ω femtosecond laser pulses in the mid-IR spectral region. Our purpose is to reveal the basic physics for a strict two-level medium and to this end the Maxwell-Bloch TLA will be considered. We will study pulses with a duration of 300 fs (with a w 5w
An ultrafast light-intensity modulator, based on stimulated Raman scattering, is described. The intensity of a continuous wave laser is fully modulated at 17THz using hydrogen in a high-finesse cavity. The modulation frequency is determined by the molecular constant of the Raman medium, i.e., the Raman shift frequency. The modulation frequency can be changed in the tetrahertz range by replacing the Raman medium. Due to the accurate modulation frequency and the high beam coherence, this device is amenable to a variety of applications such as in basic science and also in advanced industrial technology.
A critical dependence of the quantum interference on the optical Stark spectral shift produced when two-color laser pulses interact with a two-level medium is observed. The four-wave mixing of two ultrashort phase-locked $\ensuremath{\omega}\text{\ensuremath{-}}3\ensuremath{\omega}$ laser pulses propagating coherently in a two-level system depends on the pulses' relative phase. The phase dominating the efficiency of the coupling to the anti-Stokes Raman component is found to be determined by the sign of the total ac Stark shift induced in the system, in such a way that the phase sensitivity disappears precisely where the ac Stark effect due to both pulses is compensated. A coherent control scheme based on this phenomenon can be contemplated as the basis for nonlinear optical spectroscopy techniques.
We suggest that subfemtosecond pulses can be generated by using high-order stimulated Raman scattering when a Raman transition is driven by three intense single-mode laser beams with two different modulation frequencies. An oscillatory strong Raman coherence is established by the modulated molecular modulation. Numeric simulations based on the first fundamental vibrational Raman transition of gaseous and solid deuterium indicate that subfemtosecond pulses can be generated by Raman excitations with above, below, or opposite Raman detunings.
Unlike spontaneous Raman effect, nonlinear Raman scattering generates fields with a well-defined phase, allowing Raman signals from individual scatterers to add up into a highly directional, high-brightness coherent beam. Here, we show that the phase of coherent Raman scattering can be accurately controlled and finely tuned by using spectrally and temporally tailored optical driver fields. In our experiments, performed with spectrally optimized phase-tunable laser pulses, such a phase control is visualized through the interference of the coherent Raman signal with the field resulting from nonresonant four-wave mixing. This interference gives rise to Fano-type profiles in the overall nonlinear response measured as a function of the delay time between the laser pulses, featuring a well-resolved destructive-interference dip on the dark side of the Raman peak. This phase-control strategy is shown to radically enhance the coherent response from weak Raman modes, thus helping confront long-standing challenges in nonlinear Raman imaging and microspectroscopy.