Abstract Nonadiabatic effects in the nuclear dynamics of the H2+ molecular ion, initiated by ionization of the H2 molecule, is studied by means of the probability and flux distribution functions arising from the space fractional Schrödinger equation. In order to solve the fractional Schrödinger eigenvalue equation, it is shown that the quantum Riesz fractional derivative operator fulfills the usual properties of the quantum momentum operator acting on the bra and ket vectors of the abstract Hilbert space. Then, the fractional Fourier grid Hamiltonian method is implemented and applied to molecular vibrations. The eigenenergies and eigenfunctions of the fractional Schrödinger equation describing the vibrational motion of the H2+ and D2+ molecules are analyzed. In particular, it is shown that the position‐momentum Heisenberg's uncertainty relationship holds independently of the fractional Schrödinger equation. Finally, the probability and flux distributions are presented, demonstrating the applicability of the fractional Schrödinger equation for taking into account nonadiabatic effects.
Abstract Nonadiabatic effects in the nuclear dynamics of the H2+ molecular ion, initiated by ionization of the H2 molecule, is studied by means of the probability and flux distribution functions arising from the space fractional Schrödinger equation. In order to solve the fractional Schrödinger eigenvalue equation, it is shown that the quantum Riesz fractional derivative operator fulfills the usual properties of the quantum momentum operator acting on the bra and ket vectors of the abstract Hilbert space. Then, the fractional Fourier grid Hamiltonian method is implemented and applied to molecular vibrations. The eigenenergies and eigenfunctions of the fractional Schrödinger equation describing the vibrational motion of the H2+ and D2+ molecules are analyzed. In particular, it is shown that the position‐momentum Heisenberg's uncertainty relationship holds independently of the fractional Schrödinger equation. Finally, the probability and flux distributions are presented, demonstrating the applicability of the fractional Schrödinger equation for taking into account nonadiabatic effects.
When molecules move, their nuclei flow. The corresponding quantum observable, i.e., the nuclear flux density, was introduced by Schrödinger in 1926, but until now, it has not been measured. Here the first experimental results are deduced from high-resolution pump-probe measurements of the time-dependent nuclear densities in a vibrating diatomic molecule or molecular ion. The nuclear densities are converted to flux densities by means of the continuity equation. The flux densities are much more sensitive to time-dependent quantum effects than the densities. Applications to the sodium molecule and the deuterium molecular ion unravel four new effects; e.g., at the turns from bond stretch to compression, the flux of the nuclei exhibits multiple changes of directions, from small to large bond lengths, a phenomenon that we call the "quantum accordion."
This study investigates the time-fractional Schrödinger equation (TFSE) for a free particle using the Caputo fractional derivative. The model extends the classical Schrödinger equation by incorporating memory effects through a non-integer order time derivative. By applying the Fourier transform method, an explicit solution is derived in terms of the Mittag–Leffler function, which generalizes the classical exponential evolution. The analysis reveals that the resulting dynamics are non-unitary, leading to a time-dependent total probability that deviates from the conservation property of standard quantum mechanics. Numerical illustrations demonstrate the influence of the fractional order ν on wave packet evolution and probability behavior. The results highlight the role of fractional calculus in modeling non-Markovian quantum systems and provide insight into the transition from fractional to classical dynamics as v→1. .
The quantum trajectory method (QTM) is applied to nonadiabatic electronic transitions. Equations of motion in a Lagrangian framework are derived for the probability density, velocity, position, and action functions for a discretized wave packet moving along coupled potential energy surfaces. In solving these equations of motion, we obtain agreement with exact quantum results computed by solving the time-dependent Schrödinger equation on a space-fixed grid. On each of the coupled potential energy surfaces, the dynamics of the trajectories is fully quantum mechanical, i.e., there are no “surface–hopping transitions.” We present a detailed analysis of the QTM results including density changes, complex oscillations of the wave functions, phase space analysis, and a detailed discussion of the forces that contribute to the evolution the trajectories.
In this paper we propose an ab initio method to solve quantum many-body problems of molecular dynamics where both electronic and nuclear degrees are represented by ensembles of trajectories and guiding waves in physical space. Both electrons and nuclei can be treated quantum mechanically where the guiding waves obey a set of coupled Schrodinger equations (quantum-quantum description) or, alternatively, coupled Schrodinger-Newtonian equations are solved for the quantum-classical approximation. The method takes into account local and nonlocal quantum correlation effects in a self-consistent manner. The general formalism is applied to one- and two-dimensional hydrogen molecules subjected to a strong ultrashort optical pulse. Comparison is made with the results from the "exact" Ehrenfest molecular dynamics for the molecular ionization and for the evolution of the internuclear distance as the molecule dissociates.
In this paper, the fractional Schrödinger equation that contains the quantum Riesz fractional derivative instead of the Laplace operator is revisited for the case of a particle moving in the infinite potential well. In the recent papers [M. Jeng, S.-L.-Y. Xu, E. Hawkins, and J. M. Schwarz, “On the nonlocality of the fractional Schrödinger equation,” J. Math. Phys. 51, 062102 (2010)10.1063/1.3430552] and [S. S. Bayin, “On the consistency of the solutions of the space fractional Schrödinger equation,” J. Math. Phys. 53, 042105 (2012)10.1063/1.4705268] published in this journal, controversial opinions regarding solutions to the fractional Schrödinger equation for a particle moving in the infinite potential well that were derived by Laskin [“Fractals and quantum mechanics,” Chaos 10, 780–790 (2000)10.1063/1.1050284] have been given. In this paper, a thorough mathematical treatment of these matters is provided. The problem under consideration is reformulated in terms of three integral equations with the power kernels. Even if the equations look not very complicated, no solution to these equations in explicit form is known. Still, the obtained equations are used to show that the eigenvalues and eigenfunctions of the fractional Schrödinger equation for a particle moving in the infinite potential well given by Laskin [“Fractals and quantum mechanics,” Chaos 10, 780–790 (2000)10.1063/1.1050284] and many other papers by different authors cannot be valid as has been first stated by Jeng et al. [“On the nonlocality of the fractional Schrödinger equation,” J. Math. Phys. 51, 062102 (2010)10.1063/1.3430552].