Fermi's golden rule is one of the most important tools of quantum mechanics. It gives the general formula for transition rates, the rates at which particles are ‘scattered’ from one state to another by a perturbation. ‘Scattered’ is in quotation marks because it is a much more general concept than one might guess. An obvious example is provided by impurities in a crystal, which scatter an electron from one Bloch state to another. They change its momentum but not its energy. Similarly, phonons (vibrations of the lattice) also scatter electrons, but in this case they change the energy of the electrons as well as their momentum. A less obvious example is the absorption of light, which can be viewed as a scattering process in which an electron collides with a photon. The converse process also occurs, where an electron loses energy to a photon, and gives rise to spontaneous and stimulated emission. Thus scattering is a remarkably general concept. The examples suggest that there are two broad classes of scattering processes that we should treat: (i) potentials that are constant in time, such as impurities in a crystal, which do not change the energy of the particle being scattered; (ii) potentials that vary harmonically in time as cos ω q t , such as phonons and photons, which change the energy of the particle by ± ħ ω q .
Fermi's golden rule is one of the most important tools of quantum mechanics. It gives the general formula for transition rates, the rates at which particles are ‘scattered’ from one state to another by a perturbation. ‘Scattered’ is in quotation marks because it is a much more general concept than one might guess. An obvious example is provided by impurities in a crystal, which scatter an electron from one Bloch state to another. They change its momentum but not its energy. Similarly, phonons (vibrations of the lattice) also scatter electrons, but in this case they change the energy of the electrons as well as their momentum. A less obvious example is the absorption of light, which can be viewed as a scattering process in which an electron collides with a photon. The converse process also occurs, where an electron loses energy to a photon, and gives rise to spontaneous and stimulated emission. Thus scattering is a remarkably general concept. The examples suggest that there are two broad classes of scattering processes that we should treat: (i) potentials that are constant in time, such as impurities in a crystal, which do not change the energy of the particle being scattered; (ii) potentials that vary harmonically in time as cos ω q t , such as phonons and photons, which change the energy of the particle by ± ħ ω q .
We calculate the scattering rate of a quantum particle, based on Fermi’s golden rule for a quantum particle as a distribution of matter, where the density of states is a function of the particle Lagrangian, not of the Hamiltonian, as in the conventional theory based on the Schrödinger equation. Thus, the density of states does not refer to the energies as in the conventional form, but to the Lagrangian functions, which, besides the energies, include the momentum-velocity products, that are also constants of motion for the initial and the final states. We obtain the relativistic dependence on the momentum, and the two scattering rates for the two possible cases, with the spin conservation, or the spin inversion.
A novel and readily understandable derivation of the Golden Rule of time dependent perturbation theory is presented. The derivation is based on adiabatic turning on of the perturbation as used, for instance, in some formal developments of scattering theory. Energy conservation is expressed in terms of an intuitively and physically appealing Lorentzian line shape rather than the artificial, oscillatory sin(x)=x type line shape that appears in conventional derivations. The conditions for the derivation's validity are compactly and conveniently expressed in the frequency/energy domain rather than in the usual time domain. The derivation also highlights how, along with energy conservation, the transition rate faithfully and instantaneously follows the variations in the square of the perturbing potential as one may expect in the adiabatic limit. In the first instance, the adiabatic turning on is achieved, as usual, by a single exponential time variation. But we demonstrate that the instantaneous following of the square of the perturbing potential by the transition rate is more general and that one can derive the Golden Rule for a general slowly varying time dependent perturbation. This allows one to derive generalisations of the simple decay law, originally derived in the classic paper by Weisskopf and Wigner; a tutorial exposition of the essence of this classic work is provided. The Oppenheimer method for applying the Golden rule to problems, such as the electric field ionisation of atoms, in which the perturbing potential can also create the final states, is reviewed. No use of an energy gap condition is needed to derive our results on adiabatic behaviour in contrast to the origianl derivations of the adiabatic theorem in quantum mechanics.
A simple way to derive Bardeen’s tunneling theory is introduced. With a low rate of tunneling of, for example, electrons from one electrode to another through a wide vacuum gap, the appearance of the second electrode can be regarded as a perturbation. Then Bardeen’s formula for tunneling follows exactly from Fermi’s golden rule, supposing that this perturbation appears suddenly at some instant of time. Bardeen’s theory is illustrated by assuming a smoothly variable barrier shape, including the rectangular one as a limiting case. This exactly solvable example clarifies the sensitivity of the tunneling probability to the barrier shape and the energy of the tunneling particle.
Fermi's golden rule which describes the transition rates between two electronic levels under external stimulations is used ubiquitously in different fields of physics. The original Fermi's golden rule was derived from perturbative time-dependent Schrödinger's equation without the direct contribution by decoherence effect. However, as a result of recent developments of quantum computing and ultra fast carrier dynamics, the decoherence becomes a prominent topic in fundamental research.Here, by using the non-adiabatic molecular dynamics which goes beyond the time-dependent Schrödinger's equation by introducing decoherence, we study the effect of decoherence on Fermi's golden rule for the fixed basis and the adiabatic basis, respectively. We find that when the decoherence time becomes short, there is a significant deviation from the Fermi's golden rule for both bases. By using monolayer WS2 as an example, we investigate the decoherence effect in the carrier transitions induced by the electron-phonon coupling with first-principle method.
Abstract Fermi's Golden Rule is one of the most important results in quantum mechanics, predicting transition rates in applications ranging from beta decay to optical transitions, autoionization and photoionization. Most textbooks derive the Golden Rule only for the canonical case of a discrete state coupled by a time-independent perturbation to a continuum of final states. Here we present a unified treatment of several physical situations, including light absorption in atoms and solids, that all lead to the same Golden Rule expression. The essential ingredients are the transition matrix element and a spectral weighting function, whose physical origin need not be the density of final states, nor necessarily anything to do with the matter.The conventional discrete-to-continuum derivation introduces pedagogical complications associated with continuum normalization and the interpretation of the density of states. Among the cases considered here, the derivation for discrete transitions driven by a noisy perturbation is no more difficult mathematically but conceptually clearer, while leading directly to practical calculations. This suggests that it provides a more natural first introduction to the Golden Rule, with conventional continuum derivations better viewed later as another realization of the same underlying mathematical structure, rather than the other way around.
Controlling transition rates is a central objective across quantum optics, condensed-matter physics, and chemical physics, encompassing processes such as spontaneous emission, energy and charge transfer, spin relaxation, and chemical reactions. Although Fermi's golden rule provides a powerful framework for calculating such rates of weakly coupled transitions, conventional calculations require the interaction to be specified in advance; the range of rate responses attainable over a broader interaction space remains unknown. We formulate spectral-overlap golden-rule rates as quadratic forms of the interaction and derive rigorous bounds on rate modulation over a specified interaction space. As an example, application to energy transfer from a donor to a molecular vibration coupled to an optical cavity reveals that enhancement and suppression depend jointly on the interaction and cavity detuning, including continuous reversal of the rate response for a fixed interaction. The same approach may elucidate rate control for other golden-rule processes, including excitation-energy transfer, nonadiabatic electron transfer, nonradiative electronic transitions, vibrational and spin relaxation, and spontaneous emission.