Two-dimensional femtosecond optical spectroscopy of trapping dynamics in a charge-transfer process

• Published in: Chemical physics letters 2016-04, Vol.650, p.41-46
• Main Authors: Keß, Martin, Engel, Volker
• Format: Article
• Language: English
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2016.02.046

[Display omitted] •In this work we study the transfer dynamics in coupled electronic states.•A quantum-jump approach makes calculation of bath-system spectra possible.•Laser-excited states with very long lifetimes are identified.•Two-dimensional vibronic spectra exhibit signatures of the long-lived states.•Analysis of the two-dimensional spectra reveals state-selective decay dynamics. We study charge-transfer dynamics monitored by two-dimensional (2D) optical spectroscopy. The often used model consisting of two coupled diabatic electronic states in a single reaction coordinate is used to demonstrate the relation between the vibronic dynamics and the 2D-spectra. Within the employed wave-function approach, dissipation is included via a quantum-jump algorithm with explicit treatment of dephasing. States with long lifetimes which decay slowly due to the interaction with the environment are identified. Using filtered Fourier transforms, energy and time resolved information about the dissipative system dynamics can be obtained.