Fermi's golden rule explained

In quantum physics, Fermi's golden rule is a formula that describes the transition rate (the probability of a transition per unit time) from one energy eigenstate of a quantum system to a group of energy eigenstates in a continuum, as a result of a weak perturbation. This transition rate is effectively independent of time (so long as the strength of the perturbation is independent of time) and is proportional to the strength of the coupling between the initial and final states of the system (described by the square of the matrix element of the perturbation) as well as the density of states. It is also applicable when the final state is discrete, i.e. it is not part of a continuum, if there is some decoherence in the process, like relaxation or collision of the atoms, or like noise in the perturbation, in which case the density of states is replaced by the reciprocal of the decoherence bandwidth.

Historical background

Although the rule is named after Enrico Fermi, most of the work leading to it is due to Paul Dirac, who twenty years earlier had formulated a virtually identical equation, including the three components of a constant, the matrix element of the perturbation and an energy difference.^{[1] [2]} It was given this name because, on account of its importance, Fermi called it "golden rule No. 2".^[3]

Most uses of the term Fermi's golden rule are referring to "golden rule No. 2", but Fermi's "golden rule No. 1" is of a similar form and considers the probability of indirect transitions per unit time.^[4]

The rate and its derivation

|i\rangle of an unperturbed Hamiltonian and considers the effect of a perturbing Hamiltonian applied to the system. If is time-independent, the system goes only into those states in the continuum that have the same energy as the initial state. If is oscillating sinusoidally as a function of time (i.e. it is a harmonic perturbation) with an angular frequency, the transition is into states with energies that differ by from the energy of the initial state.

In both cases, the transition probability per unit of time from the initial state

|i\rangle to a set of final states |f\rangle is essentially constant. It is given, to first-order approximation, by$$\backslash Gamma\_\; =\; \backslash frac\; \backslash left|\; \backslash langle\; f|H\text{'}|i\; \backslash rangle\; \backslash right|^2\; \backslash rho(E\_f),$$where \langle f|H'|i \rangle is the matrix element (in bra–ket notation) of the perturbation between the final and initial states, and \rho(E _{f)} is the density of states (number of continuum states divided by dE in the infinitesimally small energy interval E to E + dE ) at the energy E _{f} of the final states. This transition probability is also called "decay probability" and is related to the inverse of the mean lifetime. Thus, the probability of finding the system in state |i\rangle is proportional to e ^{- \Gamma _{i} t} .

The standard way to derive the equation is to start with time-dependent perturbation theory and to take the limit for absorption under the assumption that the time of the measurement is much larger than the time needed for the transition.^{[5] [6]}

Only the magnitude of the matrix element

\langle f|H'|i \rangle enters the Fermi's golden rule. The phase of this matrix element, however, contains separate information about the transition process.It appears in expressions that complement the golden rule in the semiclassical Boltzmann equation approach to electron transport.^[9]

While the Golden rule is commonly stated and derived in the terms above, the final state (continuum) wave function is often rather vaguely described, and not normalized correctly (and the normalisation is used in the derivation). The problem is that in order to produce a continuum there can be no spatial confinement (which would necessarily discretise the spectrum), and therefore the continuum wave functions must have infinite extent, and in turn this means that the normalisation $\backslash langle\; f|f\; \backslash rangle\; =\; \backslash int\; d^3\backslash mathbf\; \backslash left|f(\backslash mathbf)\backslash right|^2$ is infinite, not unity. If the interactions depend on the energy of the continuum state, but not any other quantum numbers, it is usual to normalise continuum wave-functions with energy

\varepsilon labelled | \varepsilon\rangle , by writing \langle \varepsilon|\varepsilon ' \rangle = \delta(\varepsilon - \varepsilon ') where \delta is the Dirac delta function, and effectively a factor of the square-root of the density of states is included into |\varepsilon _{i\rangle} .^[10] In this case, the continuum wave function has dimensions of $1/\backslash sqrt$, and the Golden Rule is now$$\backslash Gamma\_\; =\; \backslash frac\; |\backslash langle\; \backslash varepsilon\_i|H\text{'}|i\backslash rangle|^2\; .$$where \varepsilon _{i} refers to the continuum state with the same energy as the discrete state i . For example, correctly normalized continuum wave functions for the case of a free electron in the vicinity of a hydrogen atom are available in Bethe and Salpeter.^[11]

Applications

Semiconductors

The Fermi's golden rule can be used for calculating the transition probability rate for an electron that is excited by a photon from the valence band to the conduction band in a direct band-gap semiconductor, and also for when the electron recombines with the hole and emits a photon.^[12] Consider a photon of frequency

\omega and wavevector bf{q} , where the light dispersion relation is \omega = (c/n)\left| bf{q}\right| and n is the index of refraction.

Using the Coulomb gauge where

\nabla ⋅ bf{A}=0 and V =0 , the vector potential of light is given by bf{A} = A ^{i ( bf{q} _{0 \boldsymbol{\varepsilon}e} ⋅ bf{r}-\omega t)} + C where the resulting electric field is$$\backslash textbf\; =\; -\backslash frac\; =\; \backslash mathrm\; \backslash omega\; A\_0\; \backslash boldsymbol\; e^.$$

For an electron in the valence band, the Hamiltonian is$$H\; =\; \backslash frac\; +\; V(\backslash textbf),$$where

V( bf{r}) is the potential of the crystal, e and m _{0} are the charge and mass of an electron, and bf{p} is the momentum operator. Here we consider process involving one photon and first order in bf{A} . The resulting Hamiltonian is$$H\; =\; H\_0\; +\; H\text{'}\; =\; \backslash left[\backslash frac\{\backslash textbf\{p\}^2\}\{2m\_0\}\; +\; V(\backslash textbf\{r\})\; \backslash right]\; +\; \backslash left[\backslash frac\{e\}\{2m\_0\}(\backslash textbf\{p\}\backslash cdot\; \backslash textbf\{A\}\; +\; \backslash textbf\{A\}\backslash cdot\; \backslash textbf\{p\})\; \backslash right],$$where H' is the perturbation of light.

From here on we consider vertical optical dipole transition, and thus have transition probability based on time-dependent perturbation theory that$$\backslash Gamma\_\; =\; \backslash frac\; \backslash left|\backslash langle\; f|H\text{'}|i\backslash rangle\; \backslash right|^2\backslash delta\; (E\_f-E\_i\; \backslash pm\; \backslash hbar\; \backslash omega),$$with $$H\text{'}\; \backslash approx\; \backslash frac\backslash boldsymbol\backslash cdot\; \backslash mathbf,$$where

\boldsymbol{\varepsilon} is the light polarization vector. |i\rangle and |f\rangle are the Bloch wavefunction of the initial and final states. Here the transition probability needs to satisfy the energyconservation given by \delta (E _{f-E} _{i} \pm \hbar \omega) . From perturbation it is evident that the heart of the calculation lies in the matrix elements shown in the bracket.

For the initial and final states in valence and conduction bands, we have

|i\rangle = \Psi _{v,bf{k} _{i,s} _{i}(bf{r})} and |f\rangle = \Psi _{c,bf{k} _{f,s} _{f}(bf{r})} , respectively and if the H' operator does not act on the spin, the electron stays in the same spin state and hence we can write the Bloch wavefunction of the initial and final states as$$\backslash Psi\_(\backslash textbf)=\backslash fracu\_(\backslash textbf)e^,$$$$\backslash Psi\_(\backslash textbf)=\backslash fracu\_(\backslash textbf)e^,$$where N is the number of unit cells with volume \Omega _{0} . Calculating using these wavefunctions, and focusing on emission (photoluminescence) rather than absorption, we are led to the transition rate$$\backslash Gamma\_=\backslash frac\backslash left(\backslash frac\backslash right)^2|\backslash boldsymbol\; \backslash cdot\; \backslash boldsymbol\_(\backslash textbf)|^2\; \backslash delta\; (E\_c\; -\; E\_v\; -\; \backslash hbar\; \backslash omega),$$where \boldsymbol{\mu} _{cv} defined as the optical transition dipole moment is qualitatively the expectation value \langle c| ( charge ) x ( distance )|v\rangle and in this situation takes the form$$\backslash boldsymbol\_\; =\; -\backslash frac\; \backslash int\_\; d\backslash textbf\text{'}\; u^*\_(\backslash textbf\text{'})\backslash nabla\; u\_(\backslash textbf\text{'}).$$

Finally, we want to know the total transition rate

\Gamma(\omega) . Hence we need to sum over all possible initial and final states that can satisfy the energy conservation (i.e. an integral of the Brillouin zone in the k-space), and take into account spin degeneracy, which after calculation results in$$\backslash Gamma(\backslash omega)\; =\; \backslash frac\backslash left(\backslash frac\; \backslash right)^2|\backslash boldsymbol\backslash cdot\; \backslash boldsymbol\_|^2\; \backslash rho\_(\backslash omega)$$where \rho _{cv} (\omega) is the joint valence-conduction density of states (i.e. the density of pair of states; one occupied valence state, one empty conduction state). In 3D, this is$$\backslash rho\_(\backslash omega)\; =\; 2\backslash pi\; \backslash left(\backslash frac\backslash right)^\backslash sqrt,$$but the joint DOS is different for 2D, 1D, and 0D.

We note that in a general way we can express the Fermi's golden rule for semiconductors as^[13] $$\backslash Gamma\_=\backslash frac\backslash int\_\backslash text\; \backslash frac|H\_\text{'}|^2\backslash delta(E\_c(\backslash textbf)\; -\; E\_v(\backslash textbf)\; -\; \backslash hbar\backslash omega).$$

In the same manner, the stationary DC photocurrent with amplitude proportional to the square of the field of light is$$\backslash textbf=-\backslash frac\backslash sum\_\backslash int\_\backslash text\; \backslash frac\; |\backslash textbf\_i-\backslash textbf\_f|(f\_i(\backslash textbf)-f\_f(\backslash textbf))|H\_\text{'}|^2\backslash delta(E\_f(\backslash textbf)\; -\; E\_i(\backslash textbf)\; -\; \backslash hbar\backslash omega),$$where

\tau is the relaxation time, bf{v} _{i-bf{v}} _{f} and f _{i(bf{k})-f} _{f(bf{k})} are thedifference of the group velocity and Fermi-Dirac distribution between possible the initial andfinal states. Here |H _{if} '| ^{2} defines the optical transition dipole. Due to the commutation relation between position bf{r} and the Hamiltonian, we can also rewrite the transition dipole and photocurrent in terms of position operator matrix using \langle i| bf{p}|f\rangle= - im _{0\omega\langle} i| bf{r}|f\rangle . This effect can only exist in systems with broken inversion symmetry and nonzero components of the photocurrent can be obtained by symmetry arguments.

Scanning tunneling microscopy

In a scanning tunneling microscope, the Fermi's golden rule is used in deriving the tunneling current. It takes the form$$w\; =\; \backslash frac\; |M|^2\; \backslash delta\; (E\_\; -\; E\_),$$where

M is the tunneling matrix element.

Quantum optics

When considering energy level transitions between two discrete states, Fermi's golden rule is written as$$\backslash Gamma\_\; =\; \backslash frac\; \backslash left|\backslash langle\; f|\; H\text{'}\; |i\; \backslash rangle\backslash right|^2\; g(\backslash hbar\backslash omega),$$where

g(\hbar\omega) is the density of photon states at a given energy, \hbar\omega is the photon energy, and \omega is the angular frequency. This alternative expression relies on the fact that there is a continuum of final (photon) states, i.e. the range of allowed photon energies is continuous.^[14]

Drexhage experiment

Fermi's golden rule predicts that the probability that an excited state will decay depends on the density of states. This can be seen experimentally by measuring the decay rate of a dipole near a mirror: as the presence of the mirror creates regions of higher and lower density of states, the measured decay rate depends on the distance between the mirror and the dipole.^{[15] [16]}

See also

• • • • • • Sargent's rule

External links

• More information on Fermi's golden rule
• Derivation of Fermi’s Golden Rule
• Time-dependent perturbation theory
• Fermi's golden rule: its derivation and breakdown by an ideal model

Notes and References

1. Book: Bransden . B. H. . Joachain . C. J. . Quantum Mechanics . 2nd . 1999 . 978-0582356917 . 443. Prentice Hall .
2. Dirac . P. A. M. . Paul Dirac . The Quantum Theory of Emission and Absorption of Radiation . . 114 . 243–265 . 1 March 1927. 767 . 10.1098/rspa.1927.0039 . 94746 . 1927RSPSA.114..243D . free . See equations (24) and (32).
3. Book: Fermi, E. . Nuclear Physics . University of Chicago Press . 1950 . 978-0226243658 . formula VIII.2
4. Book: Fermi, E. . Nuclear Physics . University of Chicago Press . 1950 . 978-0226243658 . formula VIII.19
5. http://www.ph.utexas.edu/~schwitte/PHY362L/QMnote.pdf R Schwitters' UT Notes on Derivation
6. It is remarkable in that the rate is constant and not linearly increasing in time, as might be naively expected for transitions with strict conservation of energy enforced. This comes about from interference of oscillatory contributions of transitions to numerous continuum states with only approximate unperturbed energy conservation, see Wolfgang Pauli, Wave Mechanics: Volume 5 of Pauli Lectures on Physics (Dover Books on Physics, 2000), pp. 150–151.
7. Landau, L. D., & Lifshitz, E. M. (2013). Quantum mechanics: non-relativistic theory (Vol. 3). Elsevier.
8. Book: Merzbacher, Eugen . 1998 . Quantum Mechanics . 3rd . Wiley, John & Sons, Inc. . 978-0-471-88702-7 . 19.7 . http://instrumentation.tamu.edu/~ting/other/QM_Merzbacher.pdf . Eugen Merzbacher.
9. Coordinate Shift in Semiclassical Boltzmann Equation and Anomalous Hall Effect . N. A. Sinitsyn, Q. Niu and A. H. MacDonald . Phys. Rev. B . 73 . 2006 . 075318 . cond-mat/0511310 . 10.1103/PhysRevB.73.075318 . 2006PhRvB..73g5318S . 7 . 119476624 .
10. Book: Quantum Mechanics Vol II Chapter XIII Complement D_. Cohen-Tannoudji. Claude. Diu. Bernard. Laloë. Franck. Wiley. 1977. 978-0471164333. Claude Cohen-Tannoudji.
11. Book: Bethe . Hans . Salpeter . Edwin . 1977 . Quantum Mechanics of One- and Two-Electron Atoms . Springer, Boston, MA . 978-0-306-20022-9 . Hans Bethe.
12. Book: Yu . Peter Y. . Cardona . Manuel . 2010 . Fundamentals of Semiconductors - Physics and Materials Properties . 4 . Springer . 260 . 978-3-642-00709-5 . 10.1007/978-3-642-00710-1 .
13. Edvinsson. T.. Optical quantum confinement and photocatalytic properties in two-, one- and zero-dimensional nanostructures. Royal Society Open Science. 5. 9. 2018. 180387. 2054-5703. 10.1098/rsos.180387 . 30839677. 6170533. 2018RSOS....580387E.
14. Book: Fox . Mark . Quantum Optics: An Introduction . 2006 . Oxford University Press . Oxford . 9780198566731 . 51.
15. Variation of the Fluorescence Decay Time of a Molecule in Front of a Mirror . K. H. Drexhage . H. Kuhn . F. P. Schäfer . Berichte der Bunsengesellschaft für physikalische Chemie . 72 . 329 . 1968 . 2 . 10.1002/bbpc.19680720261 . 94677437 .
16. Influence of a dielectric interface on fluorescence decay time . K. H. Drexhage . Journal of Luminescence . 1 . 693–701 . 1970 . 10.1016/0022-2313(70)90082-7. 1970JLum....1..693D .