Determination of non-adiabatic scattering wave functions in a Born-Oppenheimer model (Q2572603)

The paper deals with the time-dependent molecular Schrödinger equation given by \[ i\varepsilon^2\frac{\partial}{\partial t} \psi(x,t,\varepsilon)= \left(-\frac{\varepsilon^4}{2} \frac{\partial^2}{\partial x^2} + h(x) \right) \psi(x,t,\varepsilon) \] in \(L^2(\mathbb R;\mathbb C^m)\). \(\varepsilon>0\) denotes the usual small Born-Oppenheimer parameter, which is the fourth root of the electron mass divided by the mean nuclear mass. The electronic Hamiltonian \(h(x)\) is an \(m\times m\) selfadjoint matrix that depends on the nuclear position variable \(x\in\mathbb R\). The authors treat the case when two of the electronic levels are isolated from the rest of the electron Hamiltonian's spectrum and display an avoided crossing. In this case the leading order asymptotics of the nuclear wave functions associated with the non-adiabatic transitions, which are due to the propagation through the avoided crossing, is computed. This component is shown to be exponentially small in \(1/\varepsilon^2\) as \(\varepsilon \to 0\), because of the Landau-Zener mechanism. Moreover, it is shown that this component propagates asymptotically as a free Gaussian in the nuclear variables, and its momentum is shifted. The total transition probability for this transition and the momentum shift are both larger than one would expect from a naive approximation and energy conservation. The properties of the generalized eigenvectors of the above Hamiltonian play a central role in the proofs of the statements. The authors adapt the complex WKB-type techniques developed by \textit{A. Joye} [SIAM J. Math. Anal. 28, No. 3, 669--703 (1997; Zbl 0991.34071)] to obtain some necessary properties of these eigenvectors.