Global integration of the Schr\"odinger equation: a short iterative scheme within the wave operator formalism using discrete Fourier transforms

A global solution of the Schr\"odinger equation for explicitly time-dependent Hamiltonians is derived by integrating the non-linear differential equation associated with the time-dependent wave operator. A fast iterative solution method is proposed in which, however, numerous integrals over time have to be evaluated. This internal work is done using a numerical integrator based on Fast Fourier Transforms (FFT). The case of a transition between two potential wells of a model molecule driven by intense laser pulses is used as an illustrative example. This application reveals some interesting features of the integration technique. Each iteration provides a global approximate solution on grid points regularly distributed over the full time propagation interval. Inside the convergence radius, the complete integration is competitive with standard algorithms, especially when high accuracy is required.Comment: 25 pages, 14 figure

Development of a general time-dependent absorbing potential for the constrained adiabatic trajectory method

The Constrained Adiabatic Trajectory Method (CATM) allows us to compute solutions of the time-dependent Schr\"odinger equation using the Floquet formalism and Fourier decomposition, using matrix manipulation within a non-orthogonal basis set, provided that suitable constraints can be applied to the initial conditions for the Floquet eigenstate. A general form is derived for the inherent absorbing potential, which can reproduce any dispersed boundary conditions. This new artificial potential acting over an additional time interval transforms any wavefunction into a desired state, with an error involving exponentially decreasing factors. Thus a CATM propagation can be separated into several steps to limit the size of the required Fourier basis. This approach is illustrated by some calculations for the $H_2^+$ molecular ion illuminated by a laser pulse.Comment: 8 pages, 7 figure

Global integration of the Schr\"odinger equation within the wave operator formalism: The role of the effective Hamiltonian in multidimensional active spaces

A global solution of the Schr\"odinger equation, obtained recently within the wave operator formalism for explicitly time-dependent Hamiltonians [J. Phys. A: Math. Theor. 48, 225205 (2015)], is generalized to take into account the case of multidimensional active spaces. An iterative algorithm is derived to obtain the Fourier series of the evolution operator issuing from a given multidimensional active subspace and then the effective Hamiltonian corresponding to the model space is computed and analysed as a measure of the cyclic character of the dynamics. Studies of the laser controlled dynamics of diatomic models clearly show that a multidimensional active space is required if the wavefunction escapes too far from the initial subspace. A suitable choice of the multidimensional active space, including the initial and target states, increases the cyclic character and avoids divergences occuring when one-dimensional active spaces are used. The method is also proven to be efficient in describing dissipative processes such as photodissociation.Comment: 33 pages, 11 figure

Constrained Adiabatic Trajectory Method (CATM): a global integrator for explicitly time-dependent Hamiltonians

The Constrained Adiabatic Trajectory Method (CATM) is reexamined as an integrator for the Schr\"odinger equation. An initial discussion places the CATM in the context of the different integrators used in the literature for time-independent or explicitly time-dependent Hamiltonians. The emphasis is put on adiabatic processes and within this adiabatic framework the interdependence between the CATM, the wave operator, the Floquet and the (t,t') theories is presented in detail. Two points are then more particularly analysed and illustrated by a numerical calculation describing the $H_2^+$ ion submitted to a laser pulse. The first point is the ability of the CATM to dilate the Hamiltonian spectrum and thus to make the perturbative treatment of the equations defining the wave function possible, possibly by using a Krylov subspace approach as a complement. The second point is the ability of the CATM to handle extremely complex time-dependencies, such as those which appear when interaction representations are used to integrate the system.Comment: 15 pages, 14 figure

Controlling vibrational cooling with Zero-Width Resonances: An adiabatic Floquet approach

In molecular photodissociation, some specific combinations of laser parameters (wavelength and intensity) lead to unexpected Zero-Width Resonances (ZWR), with in principle infinite lifetimes. Their interest in inducing basic quenching mechanisms have recently been devised in the laser control of vibrational cooling through filtration strategies [O. Atabek et al., Phys. Rev. A87, 031403(R) (2013)]. A full quantum adiabatic control theory based on the adiabatic Floquet Hamiltonian is developed to show how a laser pulse could be envelop-shaped and frequency-chirped so as to protect a given initial vibrational state against dissociation, taking advantage from its continuous transport on the corresponding ZWR, all along the pulse duration. As compared with previous control scenarios actually suffering from non-adiabatic contamination, drastically different and much more efficient filtration goals are achieved. A semiclassical analysis helps in finding and interpreting a complete map of ZWRs in the laser parameter plane. In addition, the choice of a given ZWR path, among the complete series identified by the semiclassical approach, amounts to be crucial for the cooling scheme, targeting a single vibrational state population left at the end of the pulse, while all others have almost completely decayed. The illustrative example, offering the potentiality to be transposed to other diatomics, is Na2 prepared by photoassociation in vibrationally hot but translationally and rotationally cold states.Comment: 15 pages, 14 figure

Effective Hamiltonian Theory And Molecular Dynamics

INTRODUCTION: THE NEED FOR THE EFFECTIVE HAMILTONIAN APPROACH IN MOLECULAR DYNAMICS The theory of effective Hamiltonians was developed within nuclear physics in the sixties by Bloch[1] and Des Cloizeaux[2] as a method for determining the effective interactions between nucleons. Subsequently it was developed and largely used in quantum chemistry[3, 4] to overcome some limitations of both ab-initio and semi-empirical methods[5, 6] A more recent application of the theory is in molecular dynamics, where the basic processes studied are full collisions, in which energy transfers and structural modifications appear between molecular bound states and molecular continua [7], and half-collisions, in which one participating continuum is a photon continuum and the other one is an ionization or dissociation continuum [9]. Most of the recent theoretical treatments of collisions discretize the molecular continua by adding absorbing spatial boundaries and by working with a bounded ra

A multiple shooting method for the Zeeman effect

International audienc

Off-diagonal matrix elements: a modus tollens approach

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Direct calculation of off-diagonal matrix elements

International audienc

Élaboration d'un propagateur global pour l'équation de Schrödinger & Application à la photodynamique

La Méthode de la Trajectoire Adiabatique Contrainte est développée dans le but de résoudre globalementl équation de Schrödinger. Cette méthode utilise le formalisme de Floquet et une décomposition de Fourier pourdécrire les dépendances temporelles. Elle transforme ainsi un problème dynamique en un problème aux valeurspropres partiel dans un espace de Hilbert étendu au temps. Cette manipulation requiert l application decontraintes sur les conditions initiales de l état propre de Floquet recherché. Les contraintes sont appliquées parl intermédiaire d un opérateur absorbant artificiel. Cet algorithme est adapté à la description de systèmes dirigéspar des hamiltoniens dépendant explicitement du temps. Il ne souffre pas de l accumulation d erreurs au cours dutemps puisqu il fournit une solution globale ; les erreurs éventuelles proviennent de la non-complétude des basesfinies utilisées pour la description moléculaire ou temporelle et de l imperfection du potentiel absorbant dépendantdu temps nécessaire pour fixer les conditions initiales. Une forme générale de potentiel absorbant a étédéveloppée pour être en mesure d intégrer un problème avec une condition initiale quelconque. Des argumentsrelatifs au suivi adiabatique dans le cas de Hamiltoniens non-hermitiens sont également présentés. Nous insistonssur le rôle des facteurs de phase géométrique. Les méthodes développées sont appliquées à des systèmesatomiques ou moléculaires soumis à des impulsions laser intenses, en relation avec la problématique du contrôlemoléculaire. Nous considérons plusieurs exemples : modèles d atomes à deux ou trois niveaux, ion moléculairehydrogène et molécules froides de sodium.The Constrained Adiabatic Trajectory Method (CATM) allows us to compute global solutions of the time-dependent Schrödinger equation using the Floquet formalism and Fourier decomposition. The dynamical problem is thustransformed into a static problem, in the sense that the time will be included in an extended Hilbert space. Thisapproach requires that suitable constraints are applied to the initial conditions for the relevant Floquet eigenstate.The CATM is well suited to the description of systems driven by Hamiltonians with explicit and complicated timevariations. This method does not have cumulative errors and the only error sources are the non-completeness ofthe finite molecular and temporal basis sets used, and the imperfection of the time-dependent absorbing potentialwhich is essential to impose the correct initial conditions. A general form is derived for the absorbing potential,which can reproduce any dispersed boundary conditions. Arguments on adiabatic tracking in the case of nonhermitianHamiltonians are also presented. We insist on the role of geometric phase factors. The methods areapplied to atomic and molecular systems illuminated by intense laser pulses, in connection with molecular controlproblems. We study several examples : two or three-level atomic models, hydrogen molecular ion, cold sodiummolecules.BESANCON-Bib. Electronique (250560099) / SudocSudocFranceF