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Modified Fermi’s golden rule rate expressions

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0152804· OSTI ID:3011259
 [1];  [2]
  1. City Univ. of New York (CUNY), NY (United States). Queens College; Korea Institute for Advanced Study, Seoul (Korea, Republic of); Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of)
  2. Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of)
+ Show Author Affiliations
Fermi’s golden rule (FGR) serves as the basis for many expressions of spectroscopic observables and quantum transition rates. The utility of FGR has been demonstrated through decades of experimental confirmation. However, there still remain important cases where the evaluation of a FGR rate is ambiguous or ill-defined. Examples are cases where the rate has divergent terms due to the sparsity in the density of final states or time dependent fluctuations of system Hamiltonians. Strictly speaking, assumptions of FGR are no longer valid for such cases. However, it is still possible to define modified FGR rate expressions that are useful as effective rates. The resulting modified FGR rate expressions resolve a long standing ambiguity often encountered in using FGR and offer more reliable ways to model general rate processes. Finally, simple model calculations illustrate the utility and implications of new rate expressions.
Research Organization:
City Univ. of New York (CUNY), NY (United States); City Univ. of New York (CUNY), NY (United States). Queens College
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0021413
OSTI ID:
3011259
Alternate ID(s):
OSTI ID: 2421926
Report Number(s):
DOE-QC-21413-4
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 1 Vol. 159; ISSN 1089-7690; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (44)

Zwischenmolekulare Energiewanderung und Fluoreszenz journal January 1948
Promoting-mode free formalism for excited state radiationless decay process with Duschinsky rotation effect journal December 2008
Electron transfer rates in the levich and dogonadze theory of redox reactions journal November 1973
Electron transfers in chemistry and biology journal August 1985
Nonequilibrium generalization of Förster–Dexter theory for excitation energy transfer journal January 2002
Nonequilibrium Fermi’s Golden Rule Charge Transfer Rates via the Linearized Semiclassical Method journal May 2016
Spin–Vibronic Model for Quantitative Prediction of Reverse Intersystem Crossing Rate in Thermally Activated Delayed Fluorescence Systems journal November 2019
Charge Transfer in Dynamical Biosystems, or The Treachery of (Static) Images journal October 2014
Steering Electrons on Moving Pathways journal October 2009
Quantum chemical probes of electron-transfer kinetics: the nature of donor-acceptor interactions journal July 1991
Quantum effects in electron-transfer reactions journal February 1981
On the Temperature Dependence of Molecular Line Shapes Due to Linearly Coupled Phonon Bands † journal August 2002
Closed-Form Expressions of Quantum Electron Transfer Rate Based on the Stationary-Phase Approximation † journal September 2006
Theory of Excited State Decays and Optical Spectra: Application to Polyatomic Molecules journal August 2010
Correlation Function Approach to Radiationless Transitions journal October 1970
A Theory of Sensitized Luminescence in Solids journal May 1953
On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I journal May 1956
Theory of torsional non-Condon electron transfer: A generalized spin-boson Hamiltonian and its nonadiabatic limit solution journal January 2005
A phenomenological model of dynamical arrest of electron transfer in solvents in the glass-transition region journal February 2005
Excited state radiationless decay process with Duschinsky rotation effect: Formalism and implementation journal March 2007
Generalization of the Förster resonance energy transfer theory for quantum mechanical modulation of the donor-acceptor coupling journal November 2007
Theory of coherent resonance energy transfer for coherent initial condition journal October 2009
Time-dependent approaches for the calculation of intersystem crossing rates journal April 2011
Theory of multichromophoric coherent resonance energy transfer: A polaronic quantum master equation approach journal July 2011
Temperature dependent activation energy for electron transfer between biological molecules journal June 1976
Simulation of electron transfer in polar solvents: Effects of nonequilibrium initial state preparation journal March 1996
Inelastic tunneling in long-distance biological electron transfer reactions journal September 1997
Linear response in theory of electron transfer reactions as an alternative to the molecular harmonic oscillator model journal March 1999
Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices journal December 2013
General formulation of vibronic spectroscopy in internal coordinates journal February 2016
Non-Condon equilibrium Fermi’s golden rule electronic transition rate constants via the linearized semiclassical method journal June 2016
Non-Condon nonequilibrium Fermi’s golden rule rates from the linearized semiclassical method journal August 2016
Evaluating the anharmonicity contributions to the molecular excited state internal conversion rates with finite temperature TD-DMRG journal June 2021
A simple generalization of the energy gap law for nonradiative processes journal October 2021
The energy gap law for radiationless transitions in large molecules journal February 1970
Coherent quantum dynamics in donor–bridge–acceptor systems: beyond the hopping and super-exchange mechanisms journal October 2013
The Quantum Theory of the Emission and Absorption of Radiation journal March 1927
Generalized Master Equation with Non-Markovian Multichromophoric Förster Resonance Energy Transfer for Modular Exciton Densities journal October 2014
Multichromophoric Förster Resonance Energy Transfer journal May 2004
Delocalized excitons in natural light-harvesting complexes journal August 2018
Dynamically Controlled Protein Tunneling Paths in Photosynthetic Reaction Centers journal October 2000
Statistical-Mechanical Theory of Irreversible Processes. II. Response to Thermal Disturbance journal November 1957
A Mathematical Model for the Narrowing of Spectral Lines by Exchange or Motion journal May 1954
Electronic Energy Transfer in Molecular Crystals journal October 1976

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
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Bath spectral density
Chemistry
Electron transfer
Excitation energy transfer
Fermi's golden rule
Fluorescence resonance energy transfer
Marcus equation
Molecular dynamics
Nonadiabatic process
Perturbation theory
Physics
Quantum fluctuations
Quantum transition rate
Spectroscopy
Statistical fluctuations
Time dependent fluctuations