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Molecules 2019, 24(2), 231; https://doi.org/10.3390/molecules24020231

Monitoring of Nonadiabatic Effects in Individual Chromophores by Femtosecond Double-Pump Single-Molecule Spectroscopy: A Model Study

Department of Chemistry, Technische Universität München, D-85747 Garching, Germany
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Academic Editor: Jörg Fitter
Received: 9 December 2018 / Revised: 1 January 2019 / Accepted: 7 January 2019 / Published: 9 January 2019
(This article belongs to the Special Issue Single-Molecule Fluorescence Spectroscopy)
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Abstract

We explore, by theoretical modeling and computer simulations, how nonadiabatic couplings of excited electronic states of a polyatomic chromophore manifest themselves in single-molecule signals on femtosecond timescales. The chromophore is modeled as a system with three electronic states (the ground state and two non-adiabatically coupled excited states) and a Condon-active vibrational mode which, in turn, is coupled to a harmonic oscillator heat bath. For this system, we simulate double-pump single-molecule signals with fluorescence detection for different system-field interaction strengths, from the weak-coupling regime to the strong-coupling regime. While the signals are determined by the coherence of the electronic density matrix in the weak-coupling regime, they are determined by the populations of the electronic density matrix in the strong-coupling regime. As a consequence, the signals in the strong coupling regime allow the monitoring of nonadiabatic electronic population dynamics and are robust with respect to temporal inhomogeneity of the optical gap, while signals in the weak-coupling regime are sensitive to fluctuations of the optical gap and do not contain information on the electronic population dynamics. View Full-Text
Keywords: single-molecule spectroscopy; nonadiabatic dynamics; weak-field regime; strong-field regime single-molecule spectroscopy; nonadiabatic dynamics; weak-field regime; strong-field regime
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Gelin, M.F.; Palacino-González, E.; Chen, L.; Domcke, W. Monitoring of Nonadiabatic Effects in Individual Chromophores by Femtosecond Double-Pump Single-Molecule Spectroscopy: A Model Study. Molecules 2019, 24, 231.

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