Theory of femtosecond coherent double-pump single-molecule spectroscopy : application to light harvesting complexes
Gelin, Maxim F.
Date of Issue2015
School of Materials Science and Engineering
We develop a first principles theoretical description of femtosecond double-pump single-molecule signals of molecular aggregates. We incorporate all singly-excited electronic states and vibrational modes with significant electron-vibrational coupling into a system Hamiltonian and treat the ensuing system dynamics within the Davydov D1 Ansatz. The remaining intra- and inter-molecular vibrational modes are treated as a heat bath and their effect is accounted for through lineshape functions. We apply our theory to simulate single-molecule signals of the light harvesting complex II. The calculated signals exhibit pronounced oscillations of mixed electron-vibrational (vibronic) origin. Their period decreases with decreasing electron-vibrational couplings.
The journal of chemical physics
© 2015 American Institute of Physics. This is the author created version of a work that has been peer reviewed and accepted for publication by The journal of chemical physics, American Institute of Physics. It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [Article DOI: http://dx.doi.org/10.1063/1.4919240].