We study non--adiabatic transitions in scattering theory for the time dependent molecular Schroedinger equation in the Born--Oppenheimer limit. We assume the electron Hamiltonian has finitely many levels and consider the propagation of coherent states with high enough total energy. When two of the electronic levels are isolated from the rest of the electron Hamiltonian's spectrum and display an avoided crossing, we compute the component of the nuclear wave function associated with the non--adiabatic transition that is generated by propagation through the avoided crossing. This component is shown to be exponentially small in the square of the Born--Oppenheimer parameter, due to the Landau-Zener mechanism. It 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 what one would expect from a naive approximation and energy conservation.
We discuss a simple singular system in two dimension, two heavy particles interacting with a light particle via an attractive contact interaction. Although intuitively clear the actual application of the Born-Oppenheimer approximation to this problem is quite subtle. Nevertheless, with due care we show that this can be done, as a result we calculate the leading term of the Born-Oppenheimer approximation and indicate how to get the higher order corrections.
We explain why the conventional argument for deriving the time-dependent Born-Oppenheimer approximation is incomplete and review recent mathematical results, which clarify the situation and at the same time provide a systematic scheme for higher order corrections. We also present a new elementary derivation of the correct second-order time-dependent Born-Oppenheimer approximation and discuss as applications the dynamics near a conical intersection of potential surfaces and reactive scattering.
We apply the Born--Oppenheimer approximation to a harmonic diatomic molecule with one electron. We compare the exact and approximate results not only for the internal degrees of freedom but also for the motion of the center of mass. We address the problem of the permutation symmetry of identical nuclei and discuss other applications of the model and its limitations.
We present the construction of an exponentially accurate time-dependent Born-Oppenheimer approximation for molecular quantum mechanics. We study molecular systems whose electron masses are held fixed and whose nuclear masses are proportional to $ε^{-4}$, where $ε$ is a small expansion parameter. By optimal truncation of an asymptotic expansion, we construct approximate solutions to the time-dependent Schrödinger equation that agree with exact normalized solutions up to errors whose norms are bounded by $\ds C \exp(-γ/ε^2)$, for some C and $γ>0$.
We give a new reduction of a general diatomic molecular Hamiltonian, without modifying it near the collision set of nuclei. The resulting effective Hamiltonian is the sum of a smooth semiclassical pseudodifferential operator (the semiclassical parameter being the inverse of the square-root of the nuclear mass), and a semibounded operator localised in the elliptic region corresponding to the nuclear collision set. We also study its behaviour on exponential weights, and give several applications where molecular resonances appear and can be well located.
We reconsider the time-dependent Born-Oppenheimer theory with the goal to carefully separate between the adiabatic decoupling of a given group of energy bands from their orthogonal subspace and the semiclassics within the energy bands. Band crossings are allowed and our results are local in the sense that they hold up to the first time when a band crossing is encountered. The adiabatic decoupling leads to an effective Schroedinger equation for the nuclei, including contributions from the Berry connection.
We obtain a reduction scheme for the study of the quantum evolution of an atom in constant magnetic fields using the method developed by Martinez, Nenciu and Sordoni based on the construction of almost invariant subspace. In Martinez-Sordoni \cite{MaSo2} such a case is also studied but their reduced Hamiltonian includes the vector potential terms. In this paper, using the center of mass coordinates and constructing the almost invariant subspace different from theirs, we obtain the reduced Hamiltonian which does not include the vector potential terms. Using the reduced evolution we also obtain …
We consider the Born-Oppenheimer problem near conical intersection in two dimensions. For energies close to the crossing energy we describe the wave function near an isotropic crossing and show that it is related to generalized hypergeometric functions 0F3. This function is to a conical intersection what the Airy function is to a classical turning point. As an application we calculate the anomalous Zeeman shift of vibrational levels near a crossing.
The standard Born Oppenheimer theory does not give an accurate description of the wave function near points of level crossing. We give such a description near an isotropic conic crossing, for energies close to the crossing energy. This leads to the study of two coupled second order ordinary differential equations whose solution is described in terms of the generalized hypergeometric functions of the kind 0F3(;a,b,c;z). We find that, at low angular momenta, the mixing due to crossing is surprisingly large, scaling like μ^(1/6), where μis the electron to nuclear mass ratio.
We discuss a simple singular system in one dimension, two heavy particles interacting with a light particle via an attractive contact interaction. It is natural to apply Born-Oppenheimer approximation to this problem. We present a detailed discussion of this approach, the advantage of this simple model is that one can estimate the error terms self-consistently. Moreover, a Fock space approach to this problem is presented where a systematic expansion can be proposed to get higher order corrections. A slight modification of the same problem in which the light particle is relativistic is discusse…
In this article, the third of three, we analyse how the Weyl quantisation for compact Lie groups presented in the second article of this series fits with the projective-phase space structure of loop quantum gravity-type models. Thus, the proposed Weyl quantisation may serve as the main mathematical tool to implement the program of space adiabatic perturbation theory in such models. As we already argued in our first article, space adiabatic perturbation theory offers an ideal framework to overcome the obstacles that hinder the direct implementation of the conventional Born-Oppenheimer approach …
This article, as the first of three, aims at establishing the (time-dependent) Born-Oppenheimer approximation, in the sense of space adiabatic perturbation theory, for quantum systems constructed by techniques of the loop quantum gravity framework, especially the canonical formulation of the latter. The analysis presented here fits into a rather general framework, and offers a solution to the problem of applying the usual Born-Oppenheimer ansatz for molecular (or structurally analogous) systems to more general quantum systems (e.g. spin-orbit models) by means of space adiabatic perturbation th…
This paper is devoted to the asymptotics of eigenvalues for a Schrö-dinger operator in the case when the potential V does not tend to infinity at infinity. Such a potential is called degenerate. The point is that the set in the phase space where the associated hamiltonian is smaller than a fixed energy E may have an infinite volume, so that the Weyl formula which gives the behaviour of the counting function has to be revisited. We recall various results in this area, in the classical context as well as in the semi-classical one and comment the different methods. In sections 3, 4 we present our…
We perform a rigorous mathematical analysis of the bending modes of a linear triatomic molecule that exhibits the Renner-Teller effect. Assuming the potentials are smooth, we prove that the wave functions and energy levels have asymptotic expansions in powers of epsilon, where epsilon^4 is the ratio of an electron mass to the mass of a nucleus. To prove the validity of the expansion, we must prove various properties of the leading order equations and their solutions. The leading order eigenvalue problem is analyzed in terms of a parameter b, which is equivalent to the parameter originally used…
While the treatment of conical intersections in molecular dynamics generally requires nonadiabatic approaches, the Born-Oppenheimer adiabatic approximation is still adopted as a valid alternative in certain circumstances. In the context of Mead-Truhlar minimal coupling, this paper presents a new closure of the nuclear Born-Oppenheimer equation, thereby leading to a molecular dynamics scheme capturing geometric phase effects. Specifically, a semiclassical closure of the nuclear Ehrenfest dynamics is obtained through a convenient prescription for the nuclear Bohmian trajectories. The conical int…
The quantum problem of four particles in $\mathbb{R}^d$ ($d\geq 3$), with arbitrary masses $m_1,m_2,m_3$ and $m_4$, interacting through an harmonic oscillator potential is considered. This model allows exact solvability and a critical analysis of the Born-Oppenheimer approximation. The study is restricted to the ground state level. We pay special attention to the case of two equally heavy masses $m_1=m_2=M$ and two light particles $m_3=m_4=m$. It is shown that the sum of the first two terms of the Puiseux series, in powers of the dimensionless parameter $σ=\frac{m}{M}$, of the exact phase $Φ$ …
Graph-based linear scaling electronic structure theory for quantum-mechanical molecular dynamics simulations is adapted to the most recent shadow potential formulations of extended Lagrangian Born-Oppenheimer molecular dynamics, including fractional molecular-orbital occupation numbers, which enables stable simulations of sensitive complex chemical systems with unsteady charge solutions. The proposed formulation includes a preconditioned Krylov subspace approximation for the integration of the extended electronic degrees of freedom, which requires quantum response calculations for electronic s…
In this article, the second of three, we discuss and develop the basis of a Weyl quantisation for compact Lie groups aiming at loop quantum gravity-type models. This Weyl quantisation may serve as the main mathematical tool to implement the program of space adiabatic perturbation theory in such models. As we already argued in our first article, space adiabatic perturbation theory offers an ideal framework to overcome the obstacles that hinder the direct implementation of the conventional Born-Oppenheimer approach in the canonical formulation of loop quantum gravity. Additionally, we conjecture…
Computational error estimates for Born-Oppenheimer molecular dynamics with nearly crossing potential surfaces
Weierstrass Institute for Applied Analysis and Stochastics（魏尔斯特拉斯应用分析与随机性研究所）；University of Oslo（奥斯陆大学）；Kungl. Tekniska Högskolan（皇家理工学院）；University of Delaware（特拉华大学）
