2009
DOI: 10.1021/jp903970d
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Dissection of Rovibronic Structure by Polarization-Resolved Two-Color Resonant Four-Wave Mixing Spectroscopy

Abstract: A synergistic theoretical and experimental investigation of stimulated emission pumping (SEP) as implemented in the coherent framework of two-color resonant four-wave mixing (TC-RFWM) spectroscopy is presented, with special emphasis directed toward the identification of polarization geometries that can distinguish spectral features according to their attendant changes in rotational quantum numbers. A vector-recoupling formalism built upon a perturbative treatment of matter-field interactions and a state-multip… Show more

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Cited by 11 publications
(29 citation statements)
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“…A detailed description of the TC-RFWM apparatus used in these investigations has been reported elsewhere, 47 consequently, only the most salient features will be presented here. Two moderate-resolution dye lasers (o0.15 cm À1 fundamental bandwidth which could be narrowed to o0.04 cm À1 by insertion of an intracavity etalon) were pumped by the second harmonics of separate injection-seeded Nd:YAG systems that were triggered externally to ensure temporal overlap of electromagnetic fields at the sample.…”
Section: Experimental Methodsmentioning
confidence: 99%
See 1 more Smart Citation
“…A detailed description of the TC-RFWM apparatus used in these investigations has been reported elsewhere, 47 consequently, only the most salient features will be presented here. Two moderate-resolution dye lasers (o0.15 cm À1 fundamental bandwidth which could be narrowed to o0.04 cm À1 by insertion of an intracavity etalon) were pumped by the second harmonics of separate injection-seeded Nd:YAG systems that were triggered externally to ensure temporal overlap of electromagnetic fields at the sample.…”
Section: Experimental Methodsmentioning
confidence: 99%
“…To elucidate the influence of vibrational motion on large-amplitude hydron dynamics, the present work has implemented a fully coherent variant of the venerable stimulated emission pumping (SEP) technique 45 within the framework of two-color resonant four-wave mixing (TC-RFWM) spectroscopy. 46,47 This approach builds upon the basic paradigm of SEP, whereby two narrow-band sources of tunable laser light, commonly referred to as the PUMP and the DUMP, drive an inverted optical-optical double-resonance process designed to probe excited regions of the ground electronic manifold. For our TC-RFWM adaptation, a single PUMP field (i.e., having angular frequency o 1 and angular wavevector k 1 ) is fixed on a preselected rovibronic feature in the TrOH A ˜1B 48 This TC-RFWM scheme exhibits several unique characteristics, including laser-limited spectral resolution and true double-resonance response combined with high spatial, temporal, and polarization selectivity, which make it ideally suited for spectroscopic investigations of tropolone dynamics.…”
Section: Introductionmentioning
confidence: 99%
“…Even though bright transitions might substantially broaden upon saturation, they are in general well separated from the “extra lines” that are made visible at increased laser powers. Furthermore, specific linear and circular polarisation configurations of the two resonant lasers allow further enhancement or discrimination of entire families of rovibronic transitions 25 for the characterisation of perturbation effects. Considering the quantum mechanical interference for perturbed levels involving perpendicular transitions, L -uncoupling is suggested for the system and consequently a 1 u symmetry label for the O 1 state.…”
Section: Resultsmentioning
confidence: 99%
“…Although many of these features are accompanied by modest CÀOÀH bending, one in particular, 16 ða 1 Þ, involves large-amplitude motion of both shuttling hydrons (dominantly H 1 ) perpendicular to the reaction coordinate. The latter can be correlated directly to the 15 ða 1 Þ mode of the bare TrOH substrate which markedly enhances the rate of single proton transfer [49]. The methine frequencies are predicted to be very stable upon complexation (retaining 99-108% of TrOH values), the lone exception being 17 ða 1 Þ, where an inflated TrOH fundamental arises from the coupling of carbon backbone deformations.…”
Section: Calculated Vibrational Frequenciesmentioning
confidence: 96%