--- title: "Amplitude rate equations" sort_title: "Amplitude rate equations" date: 2023-01-03 categories: - Physics - Quantum mechanics layout: "concept" --- In quantum mechanics, the **amplitude rate equations** give the evolution of a quantum state in a time-varying potential. Although best known as the precursors of [time-dependent perturbation theory](/know/concept/time-dependent-perturbation-theory/), by themselves they are exact and widely applicable. Let $$\hat{H}_0$$ be the time-independent part of the total Hamiltonian, and $$\hat{H}_1$$ the time-varying part (whose contribution need not be small), so $$\hat{H}(t) = \hat{H}_0 + \hat{H}_1(t)$$. Suppose that the time-independent problem $$\hat{H}_0 \Ket{n} = E_n \Ket{n}$$ has already been solved, such that its general solution is a superposition as follows: $$\begin{aligned} \Ket{\Psi_0(t)} = \sum_{n} c_n \Ket{n} e^{- i E_n t / \hbar} \end{aligned}$$ Since these $$\Ket{n}$$ form a complete basis, the full solution for $$\hat{H}_0 + \hat{H}_1$$ can be written in the same form, but now with time-dependent coefficients $$c_n(t)$$: $$\begin{aligned} \Ket{\Psi(t)} = \sum_{n} c_n(t) \Ket{n} e^{- i E_n t / \hbar} \end{aligned}$$ We put this ansatz into the full Schrödinger equation, and use the known solution for $$\hat{H}_0$$: $$\begin{aligned} 0 &= \hat{H}_0 \Ket{\Psi(t)} + \hat{H}_1 \Ket{\Psi(t)} - i \hbar \dv{}{t}\Ket{\Psi(t)} \\ &= \sum_{n} \Big( c_n \hat{H}_0 \Ket{n} + c_n \hat{H}_1 \Ket{n} - c_n E_n \Ket{n} - i \hbar \dv{c_n}{t} \Ket{n} \Big) e^{- i E_n t / \hbar} \\ &= \sum_{n} \Big( c_n \hat{H}_1 \Ket{n} - i \hbar \dv{c_n}{t} \Ket{n} \Big) e^{- i E_n t / \hbar} \end{aligned}$$ We then take the inner product with an arbitrary stationary basis state $$\Ket{m}$$: $$\begin{aligned} 0 &= \sum_{n} \Big( c_n \matrixel{m}{\hat{H}_1}{n} - i \hbar \dv{c_n}{t} \inprod{m}{n} \Big) e^{- i E_n t / \hbar} \end{aligned}$$ Thanks to orthonormality, this moves the latter term outside the summation: $$\begin{aligned} i \hbar \dv{c_m}{t} e^{- i E_m t / \hbar} &= \sum_{n} c_n \matrixel{m}{\hat{H}_1}{n} e^{- i E_n t / \hbar} \end{aligned}$$ We divide by the left-hand exponential and define $$\omega_{mn} \equiv (E_m - E_n) / \hbar$$ to arrive at the desired set of amplitude rate equations, one for each basis state $$\ket{m}$$: $$\begin{aligned} \boxed{ i \hbar \dv{c_m}{t} = \sum_{n} c_n(t) \matrixel{m}{\hat{H}_1(t)}{n} e^{i \omega_{mn} t} } \end{aligned}$$ We have not made any approximations, so it is possible to exactly solve for $$c_n(t)$$ in some simple systems. This is worth pointing out, because these equations' most famous uses are for deriving time-dependent-perturbation theory (by making a truncated power series approximation) and [Rabi oscillation](/know/concept/rabi-oscillation/) (by making the [rotating wave approximation](/know/concept/rotating-wave-approximation/)). ## References 1. D.J. Griffiths, D.F. Schroeter, *Introduction to quantum mechanics*, 3rd edition, Cambridge.