scholarly journals Fermi’s Golden Rule and the Second Law of Thermodynamics

2020 ◽  
Vol 50 (11) ◽  
pp. 1509-1540
Author(s):  
D. Braak ◽  
J. Mannhart
Keyword(s):  
Quantum Dynamics ◽  
Transition Probabilities ◽  
Detailed Balance ◽  
Golden Rule ◽  
Second Law Of Thermodynamics ◽  
Optical Systems ◽  
Quantum Mechanical ◽  
Second Law ◽  
Fermi's Golden Rule ◽  
Fermi’S Golden Rule

AbstractWe present a Gedankenexperiment that leads to a violation of detailed balance if quantum mechanical transition probabilities are treated in the usual way by applying Fermi’s “golden rule”. This Gedankenexperiment introduces a collection of two-level systems that absorb and emit radiation randomly through non-reciprocal coupling to a waveguide, as realized in specific chiral quantum optical systems. The non-reciprocal coupling is modeled by a hermitean Hamiltonian and is compatible with the time-reversal invariance of unitary quantum dynamics. Surprisingly, the combination of non-reciprocity with probabilistic radiation processes entails negative entropy production. Although the considered system appears to fulfill all conditions for Markovian stochastic dynamics, such a dynamics violates the Clausius inequality, a formulation of the second law of thermodynamics. Several implications concerning the interpretation of the quantum mechanical formalism are discussed.

scholarly journals Fermions on wobbling kinks: normal versus quasinormal modes

2021 ◽  
Vol 2021 (9) ◽  
Author(s):  
João G. F. Campos ◽  
Azadeh Mohammadi
Keyword(s):  
Transition Probabilities ◽  
Transition Probability ◽  
Quasinormal Modes ◽  
Golden Rule ◽  
Coupling Constants ◽  
Large Coupling ◽  
Constant Rate ◽  
Fermi's Golden Rule ◽  
The Impact ◽  
Fermi’S Golden Rule

Abstract The system consisting of a fermion in the background of a wobbling kink is studied in this paper. To investigate the impact of the wobbling on the fermion-kink interaction, we employ the time-dependent perturbation theory formalism in quantum mechanics. To do so, we compute the transition probabilities between states given in terms of the Bogoliubov coefficients. We derive Fermi’s golden rule for the model, which allows the transition to the continuum at a constant rate if the fermion-kink coupling constant is smaller than the wobbling frequency. Moreover, we study the system replacing the shape mode with a quasinormal mode. In this case, the transition rate to continuum decays in time due to the leakage of the mode, and the final transition probability decreases sharply for large coupling constants in a way that is analogous to Fermi’s golden rule. Throughout the paper, we compare the perturbative results with numerical simulations and show that they are in good agreement.

scholarly journals The onset time of Fermi’s golden rule

2021 ◽  
Vol 477 (2248) ◽  
Author(s):  
V. Debierre ◽  
E. Lassalle
Keyword(s):  
Quantum Dynamics ◽  
Golden Rule ◽  
Onset Time ◽  
Frequency Interval ◽  
Resonant Frequencies ◽  
Standard Criterion ◽  
Fermi's Golden Rule ◽  
Short Times ◽  
Linear Decay ◽  
Fermi’S Golden Rule

Fermi’s golden rule describes the decay dynamics of unstable quantum systems coupled to a reservoir, and predicts a linear decay in time. Although it arises at relatively short times, the Fermi regime does not take hold in the earliest stages of the quantum dynamics. The standard criterion in the literature for the onset time of the Fermi regime is t F  ∼ 1/Δ ω , with Δ ω the frequency interval around the resonant transition frequency ω 0 of the system, over which the coupling to the reservoir does not vary appreciably. In this work, this criterion is shown to be inappropriate in general for broadband reservoirs, where the reservoir coupling spectrum takes the form R ( ω ) ∝  ω η , and for which it is found that for η  > 1, the onset time of the Fermi regime is given by t F  ∝ ( ω X / ω 0 ) η −1  × 1/ ω 0 where ω X is the high-frequency cutoff of the reservoir. Therefore, the onset of the Fermi regime can take place at times orders of magnitude larger than those predicted by the standard criterion. This phenomenon is shown to be related to the excitation of the off-resonant frequencies of the reservoir at short times. For broadband reservoirs with η  ≤ 1, and for narrowband reservoirs, it is shown that the standard criterion is correct.

Photoinduced Charge Transfer Dynamics in Carotenoid-Porphyrin-C60 Triad via the Linearized Semiclassical Nonequilibrium Fermi's Golden Rule

2020 ◽  
Author(s):  
Zhengqing Tong ◽  
Margaret S. Cheung ◽  
Barry D. Dunietz ◽  
Eitan Geva ◽  
Xiang Sun
Keyword(s):  
Charge Transfer ◽  
Golden Rule ◽  
Time Dependent ◽  
Rate Coefficients ◽  
Initial State ◽  
Photoinduced Charge Transfer ◽  
Transfer Rates ◽  
Fermi's Golden Rule ◽  
Photoinduced Charge ◽  
Fermi’S Golden Rule

The nonequilibrium Fermi’s golden rule (NE-FGR) describes the time-dependent rate coefficient for electronic transitions, when the nuclear degrees of freedom start out in a <i>nonequilibrium</i> state. In this letter, the linearized semiclassical (LSC) approximation of the NE-FGR is used to calculate the photoinduced charge transfer rates in the carotenoid-porphyrin-C<sub>60</sub> molecular triad dissolved in explicit tetrahydrofuran. The initial nonequilibrium state corresponds to impulsive photoexcitation from the equilibrated ground-state to the ππ* state, and the porphyrin-to-C<sub>60</sub> and the carotenoid-to-C<sub>60</sub> charge transfer rates are calculated. Our results show that accounting for the nonequilibrium nature of the initial state significantly enhances the transition rate of the porphyrin-to-C<sub>60</sub> CT process. We also derive the instantaneous Marcus theory (IMT) from LSC NE-FGR, which casts the CT rate coefficients in terms of a Marcus-like expression, with explicitly time-dependent reorganization energy and reaction free energy. IMT is found to reproduce the CT rates in the system under consideration remarkably well.

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