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diff --git a/source/know/concept/fermis-golden-rule/index.md b/source/know/concept/fermis-golden-rule/index.md index ea58ee6..cce8894 100644 --- a/source/know/concept/fermis-golden-rule/index.md +++ b/source/know/concept/fermis-golden-rule/index.md @@ -10,74 +10,210 @@ categories: layout: "concept" --- -In quantum mechanics, **Fermi's golden rule** expresses -the transition rate between two states of a system, -when a sinusoidal perturbation is applied -at the resonance frequency $$\omega = E_g / \hbar$$ of the -energy gap $$E_g$$. The main conclusion is that the rate is independent of -time. +Consider a general quantum system that is being affected by a sinusoidal potential. +Specifically, the system's time-independent base Hamiltonian $$\hat{H}_0$$ +is perturbed by an $$\hat{H}_1(t)$$ given by: -From [time-dependent perturbation theory](/know/concept/time-dependent-perturbation-theory/), -we know that the transition probability -for a particle in state $$\Ket{a}$$ to go to $$\Ket{b}$$ -is as follows for a sinusoidal perturbation at frequency $$\omega$$: +$$\begin{aligned} + \hat{H}_1(\vb{r}, t) + \equiv \hat{V}(\vb{r}) \cos(\omega t) + = \frac{1}{2} \hat{V}(\vb{r}) \: (e^{i \omega t} + e^{-i \omega t}) +\end{aligned}$$ + +This potential is switched on at $$t = 0$$. +Let us study the system's response using +[time-dependent perturbation theory](/know/concept/time-dependent-perturbation-theory/), +by expressing the perturbed wavefunction $$\ket{\Psi(t)}$$ +as a superposition of known eigenstates $$\ket{n}$$ of $$\hat{H}_0$$ +with time-dependent coefficient $$c_n(t)$$: $$\begin{aligned} - P_{ab} - = \frac{|V_{ba}|^2}{\hbar^2} \frac{\sin^2\!\big((\omega_{ba} - \omega) t / 2\big)}{(\omega_{ba} - \omega)^2} + \ket{\Psi(t)} + = \sum_n c_n(t) \ket{n} e^{-i E_n t / h} \end{aligned}$$ -Where $$\omega_{ba} \equiv (E_b - E_a) / \hbar$$. -If we assume that $$\Ket{b}$$ irreversibly absorbs an unlimited number of particles, -then we can interpret $$P_{ab}$$ as the "amount" of the current particle -that has transitioned since the last period $$2 \pi n / (\omega_{ba} \!-\! \omega)$$. +In the absence of $$\hat{H}_1$$, +the coefficients would simply be constants $$c_n^{(0)}$$. +Perturbation theory then states that the first-order correction +$$c_n^{(1)}(t) \approx c_n(t) - c_n^{(0)}$$ is as follows, +with $$V_{mn} \equiv \matrixel{m}{\hat{V}}{n}$$: -For generality, let $$E_b$$ be the center -of a state continuum with width $$\Delta E$$. -In that case, $$P_{ab}$$ must be modified as follows, -where $$\rho(E_x)$$ is the destination's -[density of states](/know/concept/density-of-states/): +$$\begin{aligned} + c_m^{(1)}(t) + &= - \frac{i}{2 \hbar} \sum_{n} c_n^{(0)} \: V_{mn} + \int_0^t e^{i \tau (\omega_{mn} + \omega)} + e^{i \tau (\omega_{mn} - \omega)} \dd{\tau} + \\ + &= - \frac{1}{2 \hbar} \sum_{n} c_n^{(0)} \: V_{mn} + \bigg( \frac{e^{i t (\omega_{mn} + \omega)} - 1}{\omega_{mn} + \omega} + + \frac{e^{i t (\omega_{mn} - \omega)} - 1}{\omega_{mn} - \omega} \bigg) +\end{aligned}$$ + +For simplicity, we let the system start in a known state $$\ket{a}$$, +such that $$c_n^{(0)} = \delta_{na}$$, +and we focus on a single destination state $$m = b$$, +effectively turning this into a two-level system. +Let us assume that the driving frequency is close +to that transition's resonance $$\omega \approx \omega_{ba}$$, +such that the second term is dominant over the first, which can then be neglected. +We therefore get: $$\begin{aligned} - P_{ab} - &= \frac{|V_{ba}|^2}{\hbar^2} \int_{E_b - \Delta E / 2}^{E_b + \Delta E / 2} - \frac{\sin^2\!\big((\omega_{xa} - \omega) t / 2\big)}{(\omega_{xa} - \omega)^2} \:\rho(E_x) \dd{E_x} + c_b^{(1)}(t) + &= - \frac{V_{ba}}{2 \hbar} \frac{e^{i (\omega_{ba} - \omega) t} - 1}{\omega_{ba} - \omega} + \\ + &= - i \frac{V_{ba}}{2 i \hbar} \frac{e^{i (\omega_{ba} - \omega) t / 2} - e^{- i (\omega_{ba} - \omega) t / 2}}{\omega_{ba} - \omega} \: e^{i (\omega_{ba} - \omega) t / 2} + \\ + &= - i \frac{V_{ba}}{\hbar} \frac{\sin\!\big( (\omega_{ba} - \omega) t / 2 \big)}{\omega_{ba} - \omega} \: e^{i t (\omega_{ba} - \omega) / 2} +\end{aligned}$$ + +Taking the norm squared yields the **transition probability**: +the probability that a particle starting in state $$\ket{a}$$ +will be found in $$\ket{b}$$ at time $$t > 0$$: + +$$\begin{aligned} + \boxed{ + P_{a \to b}(t) + = |c_b^{(1)}(t)|^2 + = \frac{|V_{ba}|^2}{\hbar^2} \frac{\sin^2\!\big( (\omega_{ba} - \omega) t / 2 \big)}{(\omega_{ba} - \omega)^2} + } \end{aligned}$$ -If $$E_b$$ is not in a continuum, then $$\rho(E_x) = \delta(E_x - E_b)$$. -The integrand is a sharp sinc-function around $$E_x$$. -For large $$t$$, it is so sharp that we can take out $$\rho(E_x)$$. -In that case, we also simplify the integration limits. -Then we substitute $$x \equiv (\omega_{xa}\!-\!\omega) / 2$$ to get: +This would be the same if $$\hat{H}_1 \equiv \hat{V} \sin(\omega t)$$. +However, many authors define $$\hat{H}_1 \equiv \hat{V} e^{- i \omega t}$$, +and then $$P_{a \to b}$$ is larger by a factor of $$4$$, +which can cause confusion when comparing literature. + +In any case, the probability oscillates as a function of $$t$$ +with period $$T = 2 \pi / (\omega_{ba} - \omega)$$, +so after one full period the particle is back in $$\ket{a}$$, +and after $$T/2$$ the particle is fully in $$\ket{b}$$. +See [Rabi oscillation](/know/concept/rabi-oscillation/) +for a more accurate treatment of this "flopping" behaviour. + +However, when regarded as a function of $$\omega$$, the probability +takes the form of a sinc-function centred around $$(\omega_{ba} - \omega)$$, +so it is maximized for transitions with energy +$$\hbar \omega = E_b - E_a$$. +Also notice that the sinc-function becomes narrower over time: +this has no effect if $$\omega = \omega_{ba}$$, +however, if we are slightly off-resonance, +then this means that $$P_{a \to b}$$ decreases over time. + +In fact, for $$t \to \infty$$, the sinc-function +becomes so sharp that it can be related to +the [Dirac delta function](/know/concept/dirac-delta-function/) $$\delta$$. +Consider this general identity (yes, the notation is sloppy, but it is clear): $$\begin{aligned} - P_{ab} - &\approx \frac{2}{\hbar} |V_{ba}|^2 \rho(E_b) \int_{-\infty}^\infty \frac{\sin^2(x t)}{x^2} \:dx + \lim_{t \to \infty} \frac{\sin^2(x t / 2)}{x^2} + = \frac{\pi}{2} \: \delta(x) \: t \end{aligned}$$ -This definite integral turns out to be $$\pi |t|$$, -so we find, because clearly $$t > 0$$: + +{% include proof/start.html id="proof-relation" -%} +First, observe that we can rewrite the fraction using an integral: $$\begin{aligned} - P_{ab} - &= \frac{2 \pi}{\hbar} |V_{ba}|^2 \rho(E_b) \: t + \frac{\sin(x t / 2)}{x} + = \frac{e^{i x t / 2} - e^{-i x t / 2}}{2 i x} + = \frac{i}{2 i} \int_{-t/2}^{t/2} e^{i x \tau} \dd{\tau} \end{aligned}$$ -The transition rate $$R_{ab}$$, +By taking the limit $$t \to \infty$$, +it can be turned into a nascent Dirac delta function: + +$$\begin{aligned} + \lim_{t \to \infty} \frac{\sin(x t / 2)}{x} + = \lim_{t \to \infty} \frac{\pi}{2 \pi} \int_{-\infty}^{\infty} e^{i x \tau} \dd{\tau} + = \lim_{t \to \infty} \pi \delta(x) +\end{aligned}$$ + +On the topic of the delta function, we also show that its square is given by: + +$$\begin{aligned} + \delta^2(x) + = \delta(x) \lim_{t \to \infty} \frac{1}{2 \pi} \int_{-t/2}^{t/2} e^{i x \tau} \dd{\tau} + = \delta(x) \lim_{t \to \infty} \frac{t}{2 \pi} +\end{aligned}$$ + +Where we have set $$x = 0$$ according to the first delta function. +This gives the target: + +$$\begin{aligned} + \lim_{t \to \infty} \frac{\sin^2(x t / 2)}{x^2} + = \pi^2 \delta^2(x) + = \frac{\pi}{2} \: \delta(x) \: t +\end{aligned}$$ +{% include proof/end.html id="proof-relation" %} + + +Inserting this into $$P_{a \to b}$$ +and using the general property that $$\delta(x) / c = \delta(c x)$$: + +$$\begin{aligned} + P_{a \to b} + &= \frac{\pi t}{2 \hbar^2} |V_{ba}|^2 \: \delta(\omega_{ba} - \omega) + \\ + &= \frac{\pi t}{2 \hbar} |V_{ba}|^2 \: \delta(E_b - E_a - \hbar \omega) +\end{aligned}$$ + +By taking the $$t$$-derivative, we obtain the **transition rate** $$R_{a \to b}$$, i.e. the number of particles per unit time, -then takes this form: +which is given by **Fermi's golden rule**: + +$$\begin{aligned} + \pdv{P_{a \to b}}{t} = + \boxed{ + R_{a \to b} + = \frac{\pi}{2 \hbar} |V_{ba}|^2 \: \delta(E_b - E_a - \hbar \omega) + } +\end{aligned}$$ + +Once again, beware that many authors define +$$\hat{H}_1 \equiv \hat{V} e^{- i \omega t}$$, +in which case the result is larger by a factor of $$4$$, +which can cause confusion when comparing literature. +For that alternative derivation, see the one-photon section of +[multi-photon absorption](/know/concept/multi-photon-absorption/). + +What is most noteworthy about this result is +that the $$t$$-dependence has disappeared, +and that the rate is proportional to $$|V_{ba}|^2$$, +i.e. the overlap between $$\ket{a}$$ and $$\ket{b}$$ with respect to $$\hat{V}$$. +In practice, this result is usually used inside an integral over $$\omega$$, +hence that "naked" Dirac delta function. + +For generality, let us take $$E_b$$ to be the center +of a state continuum with width $$2 W$$. +In that case, $$P_{a \to b}$$ must be modified as follows, +where $$\rho(E_x)$$ is the destination's +[density of states](/know/concept/density-of-states/): + +$$\begin{aligned} + P_{a \to b} + &= \frac{|V_{ba}|^2}{\hbar^2} \int_{E_b - W}^{E_b + W} + \frac{\sin^2\!\big((\omega_{xa} - \omega) t / 2\big)}{(\omega_{xa} - \omega)^2} \:\rho(E_x) \dd{E_x} + \\ + &= \frac{\pi t}{2 \hbar} |V_{ba}|^2 + \int_{E_b - W}^{E_b + W} \delta(E_x - E_a - \hbar \omega) \: \rho(E_x) \dd{E_x} + \\ + &= \frac{\pi t}{2 \hbar} |V_{ba}|^2 \rho(E_a + \hbar \omega) +\end{aligned}$$ + +Where we used the aforementioned relation for $$t \to \infty$$ again. +The transition rate is therefore: $$\begin{aligned} + \pdv{P_{a \to b}}{t} = \boxed{ - R_{ab} - = \pdv{P_{ab}}{t} - = \frac{2 \pi}{\hbar} |V_{ba}|^2 \rho(E_b) + R_{a \to b} + = \frac{\pi}{2 \hbar} |V_{ba}|^2 \, \rho(E_b) } \end{aligned}$$ -Note that the $$t$$-dependence has disappeared, -and all that remains is a constant factor involving $$E_b = E_a \!+\! \hbar \omega$$, -where $$\omega$$ is the resonance frequency. +This is an alternative version of Fermi's golden rule. +Unsurprisingly, if $$E_b$$ is not in a continuum, +then we simply have $$\rho(E_x) = \delta(E_b - E_x)$$ and recover the previous version. |
