Applicability criterion for semiclassical Bohmian dynamics

Within a differential expression of the Heisenberg operator, the forward and backward evolution can be joined together along a closed time contour. This manipulation leads to a dramatic cancellation of oscillations due to the two individual propagators in the Heisenberg operator and the resulting forward-backward propagator is more tractable to semiclassical approximations. This article gives a detailed description of the forward-backward semiclassical dynamics (FBSD) formalism. The semiclassical propagators, especially those of the initial value representations (IVRs), are briefly discussed. The derivation of the FBSD based on the Herman–Kluk propagator is reviewed. Different FBSD formulations with other semiclassical IVRs are worked out and numerical calculations show that they are also capable of describing quantum dynamics semiquantitatively and all display accuracy similar to the classical Wigner method.

A semi-classical propagator method combined with harmonic inversion of short time signals is used to find the resonant states of an electron interacting with a hydrogen atom near a metallic surface. The atom-electron interaction corresponds to one electron in the presence of a neutral compact core, which can be described by a simple local potential proposed by Cohen. On the other hand, the electron-surface interaction is described by a model proposed by Jennings, the so-called Jelly Model, or by a more realistic local potential that takes into account the shell structure of the metal. A semi-classical propagator approach, proposed by Herman and Kluk, is used to calculate an approximation to the autocorrelation function A(t) = <ψt|ψ0> entirely in terms of classical trajectories. A filter-diagonalization method for harmonic inversion of the complex time signal A(t) is applied to extract the resonances. We verified that the spectral analysis of the signal obtained by semi-classical methods gives satisfactory numerical results for the position and width of the lowest lying resonances.

The vibrational spectroscopy of adsorbates is becoming an important investigation tool for catalysis and material science. This paper presents a semiclassical molecular dynamics method able to reproduce the vibrational energy levels of systems composed by molecules adsorbed on solid surfaces. Specifically, we extend our divide-and-conquer semiclassical method for power spectra calculations to gas-surface systems and interface it with plane-wave electronic structure codes. The Born-Oppenheimer classical dynamics underlying the semiclassical calculation is full dimensional, and our method includes not only the motion of the adsorbate but also those of the surface and the bulk. The vibrational spectroscopic peaks related to the adsorbate are accounted together with the most coupled phonon modes to obtain spectra amenable to physical interpretations. We apply the method to the adsorption of CO, NO, and H2O on the anatase-TiO2 (101) surface. We compare our semiclassical results with the single-point harmonic estimates and the classical power spectra obtained from the same trajectory employed in the semiclassical calculation. We find that CO and NO anharmonic effects of fundamental vibrations are similarly reproduced by the classical and semiclassical dynamics and that H2O adsorption is fully and properly described in its overtone and combination band relevant components only by the semiclassical approach.

The Mixed Quantum-Classical Initial Value Representation (MQC-IVR) is a recently introduced approximate semiclassical (SC) method for the calculation of real-time quantum correlation functions. MQC-IVR employs a modified Filinov filtration (MFF) scheme to control the overall phase of the SC integrand, extending the applicability of SC methods to complex systems while retaining their ability to accurately describe quantum coherence effects. Here, we address questions regarding the effectiveness of the MFF scheme in combination with SC dynamics. Previous work showed that this filtering scheme is of limited utility in the context of semiclassical wavepacket propagation, but we find that the MFF is extraordinarily powerful in the context of correlation functions. By examining trajectory phase and amplitude contributions to the real-time SC correlation function in a model system, we clearly demonstrate that the MFF serves to reduce noise by damping amplitude only in regions of highly oscillatory phase leading to a reduction in computational effort while retaining accuracy. Further, we introduce a novel and efficient MQC-IVR formulation that allows for linear scaling in computational cost with the total simulation length, a significant improvement over the more-than quadratic scaling exhibited by the original method.

The free particle non-relativistic Schrödinger evolution of a sech wave packet, and the corresponding Wigner function and Bohmian trajectories, are studied. The overall translation and dispersion dynamics are qualitatively similar to corresponding Gaussian wave packets, as is to be expected. On the other hand, certain bizarre and completely unexpected features are also observed, such as wave packet pinching and the instantaneous formation of infinitely many nodes, despite the apparent lack of an interference source.

In this paper, Bohmian mechanics is applied to intense laser–atom physics. The motion of an atomic electron in an intense laser field is obtained from the Bohm–Newton equation. We find that the quantum potential that dominates the quantum effect of a physical system becomes negligible as the electron is driven far from the parent ion by the intense laser field, i.e. the behavior of the electron smoothly tends towards classical soon after the electron is ionized. Our numerical calculations present direct positive evidence for semiclassical trajectory methods in intense laser–atom physics where the motion of the ionized electron is treated by classical mechanics, while quantum mechanics is needed before the ionization.

The recently introduced mixed time-averaging semiclassical initial value representation of the molecular dynamics method for spectroscopic calculations [M. Buchholz, F. Grossmann, and M. Ceotto, J. Chem. Phys. 144, 094102 (2016)] is applied to systems with up to 61 dimensions, ruled by a condensed phase Caldeira-Leggett model potential. By calculating the ground state as well as the first few excited states of the system Morse oscillator, changes of both the harmonic frequency and the anharmonicity are determined. The method faithfully reproduces blueshift and redshift effects and the importance of the counter term, as previously suggested by other methods. Different from previous methods, the present semiclassical method does not take advantage of the specific form of the potential and it can represent a practical tool that opens the route to direct ab initio semiclassical simulation of condensed phase systems.

In quantum physics the free particle and the harmonically trapped particle are arguably the most important systems a physicist needs to know about. It is little known that, mathematically, they are one and the same. This knowledge helps us to understand either from the viewpoint of the other. Here we show that all general time-dependent solutions of the free-particle Schroedinger equation can be mapped to solutions of the Schroedinger equation for harmonic potentials, both the trapping oscillator and the inverted 'oscillator'. This map is fully invertible and therefore induces an isomorphism between both types of system, they are equivalent. A composition of the map and its inverse allows us to map from one harmonic oscillator to another with a different spring constant and different center position. The map is independent of the state of the system, consisting only of a coordinate transformation and multiplication by a form factor, and can be chosen such that the state is identical in both systems at one point in time. This transition point in time can be chosen freely, the wave function of the particle evolving in time in one system before the transition point can therefore be linked up smoothly with the wave function for the other system and its future evolution after the transition point. Such a cut-and-paste procedure allows us to describe the instantaneous changes of the environment a particle finds itself in. Transitions from free to trapped systems, between harmonic traps of different spring constants or center positions, or, from harmonic binding to repulsive harmonic potentials are straightforwardly modelled. This includes some time-dependent harmonic potentials. The mappings introduced here are computationally more efficient than either state-projection or harmonic oscillator propagator techniques conventionally employed when describing instantaneous (non-a 1,920 characters

Bohmian trajectories are considered for a particle that is free (i.e. the potential energy is zero), except for a half-line barrier. On the barrier, both Dirichlet and Neumann boundary conditions are considered. The half-line barrier yields one of the simplest cases of diffraction. Using the exact time-dependent propagator found by Schulman, the trajectories are computed numerically for different initial Gaussian wave packets. In particular, it is found that different boundary conditions may lead to qualitatively different sets of trajectories. In the Dirichlet case, the particles tend to be more strongly repelled. The case of an incoming plane wave is also considered. The corresponding Bohmian trajectories are compared with the trajectories of an oil drop hopping on the surface of a vibrating bath.

In Bohm's causal or trajectory interpretation of quantum mechanics, it is straightforward to determine, from a sufficiently large number of calculated particle trajectories, probability distributions for time delays caused by a potential barrier, or for transmission times through a barrier. We show that these distributions can be calculated directly and more efficiently from probability currents, without the calculation of Bohm trajectories as an intermediate step. The ideas are illustrated for Gaussian wave packets incident on a square potential barrier and used to explain why average causal delay times differ from the average delay times calculated in other approaches.

The periodically kicked Rydberg atom displays quantum localization, features of which depend on the orientation and strength of the unidirectional kicks. They include scarring of the wave function, localization by cantori, and exponential localization in the regime of strong perturbation resembling dynamical localization. Using the semiclassical Herman-Kluk propagator we investigate the degree to which semiclassical dynamics can mimic quantum localization. While the semiclassical approximation has difficulties to reproduce the scarred wave functions, the exponential tail which is a typical signature of the dynamical localization is well represented in the case of strong classical diffusion. Also the localization by broken tori is observed in the semiclassical recurrence probability for short times but the deviation from the corresponding quantum dynamics becomes more pronounced for the long-time evolution.

A wavepacket spreading under quadratic potentials is shown to have an exact classical analogue in the spreading of a classical ensemble taken from the Wigner distribution. The wavepacket motion under anharmonic potentials is complicated by greater spreading combined with additional interferences. Both are shown to be well handled by Heller’s frozen Gaussian swarm technique. Applications are outlined to spectral quantization and Franck–Condon transitions by Fourier analysis of the time correlation function. The chapter concludes with an introduction to the popular unitary Herman–Kluk coherent state propagation scheme. Advantages over semiclassical Van Vleck propagation are discussed, and a Filinov–based scheme for handling weakly chaotic systems is described.

This paper shows how a compact finite difference Hessian approximation scheme can be proficiently implemented into semiclassical initial value representation molecular dynamics. Effects of the approximation on the monodromy matrix calculation are tested by propagating initial sampling distributions to determine power spectra for analytic potential energy surfaces and for "on the fly" carbon dioxide direct dynamics. With the approximation scheme the computational cost is significantly reduced, making ab initio direct semiclassical dynamics computationally more feasible and, at the same time, properly reproducing important quantum effects inherent in the monodromy matrix and the pre-exponential factor of the semiclassical propagator.

In this work, we report a computational study of the vibrational features of four different nucleobases employing the divide-and-conquer semiclassical initial value representation molecular dynamics method. Calculations are performed on uracil, cytosine, thymine, and adenine. Results show that the overall accuracy with respect to experiments is within 20 wavenumbers, regardless of the dimensionality of the nucleobase. Vibrational estimates are accurate even in the complex case of cytosine, where two relevant conformers are taken into account. These results are promising in the perspective of future studies on more complex systems, such as nucleotides or nucleobase pairs.

Born’s rule in multiqubit Bohmian systems