Coherent dynamics in cavity femtochemistry: application of the multi-configuration time-dependent Hartree method

Abstract

The photochemistry of a molecular ensemble coupled to a resonance cavity and triggered by a femtosecond laser pulse is investigated from a real-time, quantum dynamics perspective with the multi-configuration time-dependent Hartree method. Coherent excitation of a superposition of electronic states in the ensemble leads to superradiant energy transfer to the cavity characterized by quadratic scaling with the number of molecules. Electronic decoherence associated with loss of nuclear wave packet overlap among those states destroys superradiant energy transfer, returning to a linear regime. For equal pump laser conditions, the photoexcitation probability per molecule decreases with increase of the number of molecules inside the cavity. This is caused by a loss of resonance condition of the laser with the bright electronic-photonic states of the coupled cavity-ensemble system. Increase of the laser bandwidth restores the energy transferred per molecule and the trigger probability remains independent of the number of molecules in the cavity.

13 pages, 9 figures; own accepted version

References in corpus (5)

• Multilayer multi-configuration time-dependent Hartree method: implementation and applications to a Henon-Heiles Hamiltonian and to pyrazine
• The multi-configurational time-dependent Hartree method for bosons: Many-body dynamics of bosonic systems
• Quantum Electrodynamical Density-Functional Theory: Bridging Quantum Optics and Electronic-Structure Theory
• Electronic decoherence following photoionization: full quantum-dynamical treatment of the influence of nuclear motion
• Time-dependent restricted-active-space self-consistent-field theory for laser-driven many-electron dynamics. II. Extended formulation and numerical analysis

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