title: Signatures of spatially correlated noise and non-secular effects in two-dimensional electronic spectroscopy.
abstract: We investigate how correlated fluctuations affect oscillatory features in rephasing and non-rephasing two-dimensional (2D) electronic spectra of a model dimer system. Based on a beating map analysis, we show that non-secular environmental couplings induced by uncorrelated fluctuations lead to oscillations centered at both cross- and diagonal-peaks in rephasing spectra as well as in non-rephasing spectra. Using an analytical approach, we provide a quantitative description of the non-secular effects in terms of the Feynman diagrams and show that the environment-induced mixing of different inter-excitonic coherences leads to oscillations in the rephasing diagonal-peaks and non-rephasing cross-peaks. We demonstrate that as correlations in the noise increase, the lifetime of oscillatory 2D signals is enhanced at rephasing cross-peaks and non-rephasing diagonal-peaks, while the other non-secular oscillatory signals are suppressed. We discuss that the asymmetry of 2D lineshapes in the beating map provides information on the degree of correlations in environmental fluctuations. Finally we investigate how the oscillatory features in 2D spectra are affected by inhomogeneous broadening.
authors.affiliation: Institut für Theoretische Physik, Universität Ulm, Albert-Einstein-Allee 11, Ulm D-89069, Germany.
authors.forename: James
authors.initials: J
authors.lastname: Lim
authors.affiliation: Chemical and Quantum Physics, School of Applied Sciences, RMIT University, Melbourne, Victoria 3001, Australia.
authors.forename: David J
authors.initials: DJ
authors.lastname: Ing
authors.affiliation: Institut für Theoretische Physik, Universität Ulm, Albert-Einstein-Allee 11, Ulm D-89069, Germany.
authors.forename: Joachim
authors.initials: J
authors.lastname: Rosskopf
authors.affiliation: Chemical and Quantum Physics, School of Applied Sciences, RMIT University, Melbourne, Victoria 3001, Australia.
authors.forename: Jan
authors.initials: J
authors.lastname: Jeske
authors.affiliation: Chemical and Quantum Physics, School of Applied Sciences, RMIT University, Melbourne, Victoria 3001, Australia.
authors.forename: Jared H
authors.initials: JH
authors.lastname: Cole
authors.affiliation: Institut für Theoretische Physik, Universität Ulm, Albert-Einstein-Allee 11, Ulm D-89069, Germany.
authors.forename: Susana F
authors.initials: SF
authors.lastname: Huelga
authors.affiliation: Institut für Theoretische Physik, Universität Ulm, Albert-Einstein-Allee 11, Ulm D-89069, Germany.
authors.forename: Martin B
authors.initials: MB
authors.lastname: Plenio