Theory of femtosecond coherent double-pump single-molecule spectroscopy: Application to light harvesting complexes.
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 exciton-phonon 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 periods decrease with decreasing exciton-phonon coupling.
Division of Materials Science, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798.
Lipeng
L
Chen
Department of Chemistry, Technische Universität München, Garching D-85747, Germany.
Maxim F
MF
Gelin
Department of Chemistry, Technische Universität München, Garching D-85747, Germany.
Wolfgang
W
Domcke
Division of Materials Science, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798.
Yang
Y
Zhao