Energy transfer from dark states: a relativistic approach

Area of Science:

• Quantum Chemistry
• Theoretical Physics
• Spectroscopy

Background:

• A relativistic theory for energy transfer has been developed, applicable to various energy regimes.
• This theory accounts for long-range phenomena crucial at high transferred energies.
• It also describes retardation and magnetic effects at smaller and intermediate energies.

Purpose of the Study:

• To derive leading terms for energy transfer from donor dark states using relativistic theory.
• To analyze the significance of relativistic effects at small and intermediate excess energies.
• To investigate energy transfer in interatomic and intermolecular coulombic decay (ICD).

Main Methods:

• Starting from general relativistic expressions for asymptotic contributions.
• Deriving leading-order terms for energy transfer at small and intermediate excess energies.
• Comparing the impact of Coulomb, retardation, and magnetic interactions.

Main Results:

• At small excess energies, relativistic effects (retardation, magnetic) are negligible compared to Coulomb interaction.
• For intermediate energies (hundreds of eV), retardation effects become as relevant as Coulomb interaction.
• At higher intermediate energies, retardation can dominate Coulomb interaction, and magnetic effects may become significant.

Conclusions:

• Relativistic effects are essential for accurately describing energy transfer at intermediate excess energies.
• The developed theory provides a framework for understanding phenomena like ICD.
• Non-relativistic descriptions of donor/acceptor systems are sufficient, but relativistic transfer dynamics are needed.