Vibrational coherence transfer characterized with Fourier-transform 2D IR spectroscopy

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139.
The Journal of Chemical Physics (Impact Factor: 2.95). 08/2004; 121(1):362-73. DOI: 10.1063/1.1756870
Source: PubMed


Two-dimensional infrared (2D IR) spectroscopy of the symmetric and asymmetric C[Triple Bond]O stretching vibrations of Rh(CO)(2)acac in hexane has been used to investigate vibrational coherence transfer, dephasing, and population relaxation in a multilevel vibrational system. The transfer of coherence between close-lying vibrational frequencies results in extra relaxation-induced peaks in the 2D IR spectrum, whose amplitude depends on the coherence transfer rate. Coherence transfer arises from the mutual interaction of the bright CO stretches with dark states, which in this case reflects the mutual d-pi(*) back bonding of the Rh center to both the terminal carbonyls and the acetylacenonate ligand. For 2D IR relaxation experiments with variable waiting times, coherent dynamics lead to the modulation of peak amplitudes, while incoherent population relaxation and exchange results in the growth of the relaxation-induced peaks. We have modeled the data by propagating the density matrix with the Redfield equation, incorporating all vibrational relaxation processes during all three experimental time periods and including excitation reorientation effects arising from relaxation. Coherence and population transfer time scales from the symmetric to the asymmetric stretch were found to be 350 fs and 3 ps, respectively. We also discuss a diagrammatic approach to incorporating all vibrational relaxation processes into the nonlinear response function, and show how coherence transfer influences the analysis of structural variables from 2D IR spectroscopy.

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    • "On the other hand, femtosecond timescales can be easily accessed with ultrafast optical techniques. Examples of phenomena studied via MDOS are vast and include molecular reorientation processes and solvation dynamics [8] [9], electron transfer [10], vibrational coherences in organometallic complexes [11] [12] [13] or halogens in rare gas matrices [14] [15], phonon dynamics in carbon nanotubes [16], protein unfolding kinetics [17], excitonic dynamics in light-harvesting systems [18] [19] [20] [21] [22] [23] and organic polymers [24] [25], as well as many-body physics in semiconductor quantum wells [26] [27] [28] and quantum dots [29]. "
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