dorsal/arxiv
View SchemaElectronic coherence in mixed-valence systems: Spectral analysis
| Authors | Y. Jung, R. J. Silbey, J. Cao |
|---|---|
| Categories | |
| ArXiv ID | physics/0008164 |
| URL | https://arxiv.org/abs/physics/0008164 |
| Journal | J. Phys. Chem.A, vol.103, 9460-9468 (1999) |
Abstract
The electron transfer kinetics of mixed-valence systems is studied via solving the eigen-structure of the two-state non-adiabatic diffusion operator for a wide range of electronic coupling constants and energy bias constants. The calculated spectral structure consists of three branches in the eigen-diagram, a real branch corresponding to exponential or multi-exponential decay and two symmetric branches corresponding to population oscillations between donor and acceptor states. The observed electronic coherence is shown as a result of underdamped Rabi oscillations in an overdamped solvent environment. The time-evolution of electron population is calculated by applying the propagator constructed from the eigen-solution to the non-equilibrium initial preparation, and it agrees perfectly with the result of a direct numerical propagation of the density matrix. The resulting population dynamics confirms that increasing the energy bias destroys electronic coherence.
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"abstract": "The electron transfer kinetics of mixed-valence systems is studied via\nsolving the eigen-structure of the two-state non-adiabatic diffusion operator\nfor a wide range of electronic coupling constants and energy bias constants.\nThe calculated spectral structure consists of three branches in the\neigen-diagram, a real branch corresponding to exponential or multi-exponential\ndecay and two symmetric branches corresponding to population oscillations\nbetween donor and acceptor states. The observed electronic coherence is shown\nas a result of underdamped Rabi oscillations in an overdamped solvent\nenvironment. The time-evolution of electron population is calculated by\napplying the propagator constructed from the eigen-solution to the\nnon-equilibrium initial preparation, and it agrees perfectly with the result of\na direct numerical propagation of the density matrix. The resulting population\ndynamics confirms that increasing the energy bias destroys electronic\ncoherence.",
"arxiv_id": "physics/0008164",
"authors": [
"Y. Jung",
"R. J. Silbey",
"J. Cao"
],
"categories": [
"physics.chem-ph",
"cond-mat.stat-mech"
],
"journal_ref": "J. Phys. Chem.A, vol.103, 9460-9468 (1999)",
"title": "Electronic coherence in mixed-valence systems: Spectral analysis",
"url": "https://arxiv.org/abs/physics/0008164"
},
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