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The Journal of Chemical Physics

Electronic and vibrational coherence effects in broadband transient absorption spectroscopy with chirped supercontinuum probing

Alexander L. Dobryakov, Sergey A. Kovalenko, Nikolaus P. Ernsting

Published Jun 30, 2003• 48 citations
Publisher

Abstract

The theory of transient absorption with chirped supercontinuum probing is developed for electronic excitation of a vibronic four-level scheme. Dephasing is modeled as homogeneous in the Bloch approximation together with inhomogeneous broadening. The time correction routine for transient spectra is shown to be identical to that of the nonresonant case which was treated previously. Contributions from sequential and coherent terms are calculated and compared to each other. The simulated data reveal how electronic and vibrational dephasing, detuning, and inhomogeneous broadening manifest themselves in the coherent component of femtosecond transient absorption spectra.

DOI
10.1063/1.1579672

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The theory of transient absorption with chirped supercontinuum probing is developed for electronic excitation of a vibronic four-level scheme. Dephasing is modeled as homogeneous in the Bloch approximation together with inhomogeneous broadening. The time correction routine for transient spectra is shown to be identical to that of the nonresonant case which was treated previously. Contributions from sequential and coherent terms are calculated and compared to each other. The simulated data reveal how electronic and vibrational dephasing, detuning, and inhomogeneous broadening manifest themselves in the coherent component of femtosecond transient absorption spectra.
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The role of weakly chirped pulses (time bandwidth product, DeltanuDeltatau<0.61) on three-pulse photon echo signals has been systematically studied. Pulses with varying chirp were characterized with frequency resolved optical gating (FROG) and used to measure spectrally resolved three-pulse photon echoes of a dye in solution. The weakly chirped pulses give rise to markedly different echo signals for population times below approximately 100 fs. The chirped pulses can decrease or enhance spectral signatures of an excited state absorption transition in the echo signal. Furthermore, the observed dephasing dynamics depend on the phase of the electric fields. Simulations based on a three-level model and the electric fields retrieved from the FROG traces give a good agreement for photon echo experiments with both transform limited and chirped pulses. The simulations also allow for a numerical investigation of effects of chirp in two-dimensional spectroscopy. For a two-level system, the chirped pulses result in nonelliptical two-dimensional spectra that can erroneously be interpreted as spectral heterogeneity with frequency dependent dephasing dynamics. Furthermore, chirped pulses can give rise to "false" cross peaks when strong vibrational modes are involved in the system-bath interaction.
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