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Modified Fermi's golden rule rate expressions.

Seogjoo J Jang1,2,3, Young Min Rhee3

  • 1Department of Chemistry and Biochemistry, Queens College, City University of New York, 65-30 Kissena Boulevard, Queens, New York 11367, USA and PhD Programs in Chemistry and Physics, Graduate Center of the City University of New York, New York, New York 10016, USA.

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Summary
This summary is machine-generated.

Fermi's golden rule (FGR) provides quantum transition rates but can be ill-defined. Modified FGR expressions offer effective rates, resolving ambiguities and improving models for general rate processes.

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Area of Science:

  • Quantum mechanics
  • Spectroscopy
  • Chemical physics

Background:

  • Fermi's golden rule (FGR) is fundamental for calculating quantum transition rates and spectroscopic observables.
  • Despite its wide applicability and experimental validation, FGR encounters limitations in specific scenarios.

Purpose of the Study:

  • To address ambiguities and ill-defined situations in FGR calculations.
  • To develop modified FGR rate expressions that serve as effective rates for complex systems.

Main Methods:

  • Investigating cases where FGR assumptions are violated, such as divergent terms due to sparse final states or time-dependent Hamiltonian fluctuations.
  • Deriving and defining modified FGR rate expressions.

Main Results:

  • Identified scenarios where standard FGR is inadequate, leading to ambiguous or ill-defined rates.
  • Developed novel modified FGR rate expressions that provide effective rates.
  • Demonstrated the utility of these new expressions through model calculations.

Conclusions:

  • Modified FGR rate expressions offer a robust solution to long-standing ambiguities in rate process modeling.
  • These enhanced expressions provide more reliable methods for describing general rate processes in quantum systems.