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Issue 46, 2015
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Spectral lineshapes in nonlinear electronic spectroscopy

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Abstract

We outline a computational approach for nonlinear electronic spectra, which accounts for the electronic energy fluctuations due to nuclear degrees of freedom and explicitly incorporates the fluctuations of higher excited states, induced by the dynamics in the photoactive state(s). This approach is based on mixed quantum-classical dynamics simulations. Tedious averaging over multiple trajectories is avoided by employing the linearly displaced Brownian harmonic oscillator to model the correlation functions. The present strategy couples accurate computations of the high-lying excited state manifold with dynamics simulations. The application is made to the two-dimensional electronic spectra of pyrene, a polycyclic aromatic hydrocarbon characterized by an ultrafast (few tens of femtoseconds) decay from the bright S2 state to the dark S1 state. The spectra for waiting times t2 = 0 and t2 = 1 ps demonstrate the ability of this approach to model electronic state fluctuations and realistic lineshapes. Comparison with experimental spectra [Krebs et al., New Journal of Physics, 2013, 15, 085016] shows excellent agreement and allows us to unambiguously assign the excited state absorption features.

Graphical abstract: Spectral lineshapes in nonlinear electronic spectroscopy

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Supplementary files

Article information


Submitted
26 Feb 2015
Accepted
02 Jun 2015
First published
02 Jun 2015

Phys. Chem. Chem. Phys., 2015,17, 30925-30936
Article type
Paper
Author version available

Spectral lineshapes in nonlinear electronic spectroscopy

A. Nenov, A. Giussani, B. P. Fingerhut, I. Rivalta, E. Dumont, S. Mukamel and M. Garavelli, Phys. Chem. Chem. Phys., 2015, 17, 30925
DOI: 10.1039/C5CP01167A

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