Nonadiabatic Limit Research Articles

Electronic friction near metal surface: Incorporating nuclear quantum effect with ring polymer molecular dynamics.

The molecular dynamics with electronic friction (MDEF) approach can accurately describe nonadiabatic effects at metal surfaces in the weakly nonadiabatic limit. That being said, the MDEF approach treats nuclear motion classically such that the nuclear quantum effects are completely missing in the approach. To address this limitation, we combine Electronic Friction with Ring Polymer Molecular Dynamics (EF-RPMD). In particular, we apply the averaged electronic friction from the metal surface to the centroid mode of the ring polymer. We benchmark our approach against quantum dynamics to show that EF-RPMD can accurately capture zero-point energy as well as transition dynamics. In addition, we show that EF-RPMD can correctly predict the electronic transfer rate near metal surfaces in the tunneling limit as well as the barrier crossing limit. We expect that our approach will be very useful to study nonadiabatic dynamics near metal surfaces when nuclear quantum effects become essential.

Mitigation of resistive drift wave and ion temperature gradient instabilities by velocity shear

The effects of velocity shear on the resistive drift wave instability in the non-adiabatic limit and the toroidal ion temperature gradient instability are investigated for a plasma of inhomogeneous density/ion temperature, respectively. For the resistive drift wave, we find that the instability growth rate decreases monotonically with increasing magnitude of shear, but we find that complete stabilization is impossible. For the ion temperature gradient instability, we find that the standard WKB approximation is insufficient to describe the full behavior of the instability, and that an analysis of the localized eigenmode problem reveals two separate unstable solutions, which the WKB approximation does not predict. The impact of flow shear on these two new unstable solutions is discussed. In both resistive drift wave and ion temperature gradient instabilities, the sheared flow causes a shifting, tilting, and sharpening of the electrostatic potential eddies.

(Ann. Phys. 4/2023)

Annalen der PhysikVolume 535, Issue 4 2370007 Cover PictureFree Access (Ann. Phys. 4/2023) First published: 13 April 2023 https://doi.org/10.1002/andp.202370007AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Graphical Abstract Quantum Pumping When quasiparticles of Weyl/multi-Weyl and nodal-line semimetals are subjected to a time-periodic potential well, the presence of the oscillating potential of frequency ω creates equispaced Floquet side-bands. Using the Floquet theory and the scattering matrix approach, in the zero-temperature non-adiabatic pumping limit, characteristic Fano resonance patterns are found in the transmission coefficients, which depend on the nature of the dispersion. See article number 2200460 for more details. Volume535, Issue4April 20232370007 RelatedInformation

A phase-space semiclassical approach for modeling nonadiabatic nuclear dynamics with electronic spin.

Chemical relaxation phenomena, including photochemistry and electron transfer processes, form a vigorous area of research in which nonadiabatic dynamics plays a fundamental role. However, for electronic systems with spin degrees of freedom, there are few if any applicable and practical quasiclassical methods. Here, we show that for nonadiabatic dynamics with two electronic states and a complex-valued Hamiltonian that does not obey time-reversal symmetry (as relevant to many coupled nuclear-electronic-spin systems), the optimal semiclassical approach is to generalize Tully's surface hopping dynamics from coordinate space to phase space. In order to generate the relevant phase-space adiabatic surfaces, one isolates a proper set of diabats, applies a phase gauge transformation, and then diagonalizes the total Hamiltonian (which is now parameterized by both R and P). The resulting algorithm is simple and valid in both the adiabatic and nonadiabatic limits, incorporating all Berry curvature effects. Most importantly, the resulting algorithm allows for the study of semiclassical nonadiabatic dynamics in the presence of spin-orbit coupling and/or external magnetic fields. One expects many simulations to follow as far as modeling cutting-edge experiments with entangled nuclear, electronic, and spin degrees of freedom, e.g., experiments displaying chiral-induced spin selectivity.

Analytical solution of stochastic resonance in the nonadiabatic regime.

We generalize stochastic resonance to the nonadiabatic limit by treating the double-well potential using two quadratic potentials. We use a singular perturbation method to determine an approximate analytical solution for the probability density function that asymptotically connects local solutions in boundary layers near the two minima with those in the region of the maximum that separates them. The validity of the analytical solution is confirmed numerically. Free from the constraints of the adiabatic limit, the approach allows us to predict the escape rate from one stable basin to another for systems experiencing a more complex periodic forcing.

Floquet scattering of quadratic band-touching semimetals through a time-periodic potential well

We consider tunneling of quasiparticles through a rectangular quantum well, subject to periodic driving. The quasiparticles are the itinerant charges in two-dimensional and three-dimensional semimetals having a quadratic bandtouching (QBT) point in the Brillouin zone. To analyze the time-periodic Hamiltonian, we assume a non-adiabatic limit where the Floquet theorem is applicable. By deriving the Floquet scattering matrices, we chalk out the transmission and shot noise spectra of the QBT semimetals. The spectra show Fano resonances, which we identify with the (quasi)bound states of the systems.

Exact eigenenergies of a model of vibronically coupled electron transfer reactions.

We present the first exact solution to the time-independent Schrödinger equation of a model Hamiltonian consisting of a vibrational mode coupled to three electronic states. This Hamiltonian serves as a generic model for photo-induced electronic transfer reactions. The solution is non-perturbative and can be applied to ET reactions with weak and strong electronic and vibrational coupling strengths. This work suggests a new direction towards understanding the vibronic effects in ET dynamics beyond the non-adiabatic limit and Condon approximation.

Crossover between the adiabatic and nonadiabatic electron transfer limits in the Landau-Zener model

The semiclassical models of nonadiabatic transition were proposed first by Landau and Zener in 1932, and have been widely used in the study of electron transfer (ET); however, experimental demonstration of the Landau-Zener formula remains challenging to observe. Herein, employing the Hush-Marcus theory, thermal ET in mixed-valence complexes {[Mo2]-(ph)n-[Mo2]}+ (n = 1–3) has been investigated, spanning the nonadiabatic throughout the adiabatic limit, by analysis of the intervalence transition absorbances. Evidently, the Landau-Zener formula is valid in the adiabatic regime in a broader range of conditions than the theoretical limitation known as the narrow avoided-crossing. The intermediate system is identified with an overall transition probability (κel) of ∼0.5, which is contributed by the single and the first multiple passage. This study shows that in the intermediate regime, the ET kinetic results derived from the adiabatic and nonadiabatic formalisms are nearly identical, in accordance with the Landau-Zener model. The obtained insights help to understand and control the ET processes in biological and chemical systems.

Emergent topology under slow nonadiabatic quantum dynamics

Characterization of equilibrium topological quantum phases by non-equilibrium quench dynamics provides a novel and efficient scheme in detecting topological invariants defined in equilibrium. Nevertheless, most of the previous studies have focused on the ideal sudden quench regime. Here we provide a generic non-adiabatic protocol of slowly quenching the system Hamiltonian, and investigate the non-adiabatic dynamical characterization scheme of topological phase. The {\it slow} quench protocol is realized by introducing a Coulomb-like Landau-Zener problem, and it can describe, in a unified way, the crossover from sudden quench regime (deep non-adiabatic limit) to adiabatic regime. By analytically obtaining the final state vector after non-adiabatic evolution, we can calculate the time-averaged spin polarization and the corresponding topological spin texture. We find that the topological invariants of the post-quench Hamiltonian are characterized directly by the values of spin texture on the band inversion surfaces. Compared to the sudden quench regime, where one has to take an additional step to calculate the {\it gradients} of spin polarization, this non-adiabatic characterization provides a {\it minimal} scheme in detecting the topological invariants. Our findings are not restricted to 1D and 2D topological phases under Coulomb-like quench protocol, but are also valid for higher dimensional system or different quench protocol.

Dark matter axion detection in the radio/mm waveband

We discuss axion dark matter detection via two mechanisms: spontaneous decays and resonant conversion in neutron star magnetospheres. For decays, we show that the brightness temperature signal, rather than flux, is a less ambiguous measure for selecting candidate objects. This is owing principally to the finite beam width of telescopes which prevents one from being sensitive to the total flux from the object. With this in mind, we argue that the large surface-mass-density of the galactic centre or the Virgo cluster centre offers the best chance of improving current constraints on the axion-photon coupling via spontaneous decays. For the neutron star case, we first carry out a detailed study of mixing in magnetised plasmas. We derive transport equations for the axion-photon system via a controlled gradient expansion, allowing us to address inhomogeneous mass-shell constraints for arbitrary momenta. We then derive a non-perturbative Landau-Zener formula for the conversion probability valid across the range of relativistic and non-relativistic axions and show that the standard perturbative resonant conversion amplitude is a truncation of this result in the non-adiabatic limit. Our treatment reveals that that infalling dark matter axions typically convert non-adiabatically in magnetospheres. We describe the limitations of one-dimensional mixing equations and explain how three-dimensional effects activate new photon polarisations, including longitudinal modes and illustrate these arguments with numerical simulations in higher dimensions. We find that the bandwidth of the radio signal is dominated by Doppler broadening from the relative motion of the neutron star with respect to the observer. Therefore, we conclude that the radio signal from the resonant decay is weaker than previously thought, which means one relies on local density peaks to probe weaker axion-photon couplings.

No anomalous canonical commutators induced by Berry’s phase

The monopole-like singularity of Berry’s adiabatic phase in momentum space and associated anomalous Poisson brackets have been recently discussed in various fields. With the help of the results of an exactly solvable version of Berry’s model, we show that Berry’s phase does not lead to the deformation of the principle of quantum mechanics in the sense of anomalous canonical commutators. If one should assume Berry’s phase of genuine Dirac monopole-type, which is assumed to hold not only in the adiabatic limit but also in the non-adiabatic limit, the deformation of the principle of quantum mechanics could take place. But Berry’s phase of the genuine Dirac monopole-type is not supported by the exactly solvable version of Berry’s model nor by a generic model of Berry’s phase. Besides, the monopole-like Berry’s phase in momentum space has a magnetic charge eM=2πħ, for which the possible anomalous term in the canonical commutator [xk,xl]=iħΩkl would become of the order O(ħ2).

Pathways for Single-Shot All-Optical Switching of Magnetization in Ferrimagnets

We resolve a significant controversy about how to understand and engineer single-shot all-optical switching of magnetization in ferrimagnets using femto- or picosecond-long heat pulses. By realistically modelling a generic ferrimagnet as two coupled macrospins, we comprehensively show that the net magnetization can be reversed via different pathways, using a heat pulse with duration spanning all relevant timescales within the non-adiabatic limit. This conceptual understanding is fully validated by experiments studying the material and optical limits at which the switching process in GdFeCo alloys loses its reliability. Our interpretation and results constitute a blueprint for understanding how deterministic all-optical switching can be achieved in alternative ferrimagnets using short thermal pulses.

Nonadiabatic escape and stochastic resonance

We analyze the fluctuation-driven escape of particles from a metastable state under the influence of a weak periodic force. We develop an asymptotic method to solve the appropriate Fokker–Planck equation with mixed natural and absorbing boundary conditions. The approach uses two boundary layers flanking an interior region; most of the probability is concentrated within the boundary layer near the metastable point of the potential and particles transit the interior region before exiting the domain through the other boundary layer, which is near the unstable maximal point of the potential. The dominant processes in each region are given by approximate time-dependent solutions matched to construct the approximate composite solution, which gives the rate of escape with weak periodic forcing. Using reflection we extend the method to a double well potential influenced by white noise and weak periodic forcing, and thereby derive a two-state stochastic model—the simplest treatment of stochastic resonance theory—in the nonadiabatic limit.

Chiral Induction on the Ultrafast Event of Excited State Proton Transfer Can Probe Its Mechanism

AbstractWhen protonic motion is explained as a purely quantum mechanical phenomenon, two extreme situations can be visualized as either the adiabatic or the nonadiabatic limit of proton transfer (PT). Strong orbital coupling between the donor and the acceptor pair in the proton transfer step drives PT mechanism in the adiabatic limit whereas in nonadiabatic limit PT predominantly occurs through tunneling. Here we proposed a unique way to experimentally observe the adiabaticity of PT by introducing chirality in the reaction coordinate of excited state proton transfer (ESPT). We successfully established the existence of prominent role of diastereomerism in the ESPT by both steady state and femtosecond time‐resolved transient absorption spectroscopic measurements in the adiabatic limit. The presented novel approach can overcome the limitations of only available experimental technique, i. e. kinetic isotope effect, to elucidate proton transfer mechanism.

On the calculation of quantum mechanical electron transfer rates.

We present a simple interpolation formula for the rate of an electron transfer reaction as a function of the electronic coupling strength. The formula only requires the calculation of Fermi golden rule and Born-Oppenheimer rates and so can be combined with any methods that are able to calculate these rates. We first demonstrate the accuracy of the formula by applying it to a one dimensional scattering problem for which the exact quantum mechanical, Fermi golden rule, and Born-Oppenheimer rates are readily calculated. We then describe how the formula can be combined with the Wolynes theory approximation to the golden rule rate, and the ring polymer molecular dynamics (RPMD) approximation to the Born-Oppenheimer rate, and used to capture the effects of nuclear tunneling, zero point energy, and solvent friction on condensed phase electron transfer reactions. Comparison with exact hierarchical equations of motion results for a demanding set of spin-boson models shows that the interpolation formula has an error comparable to that of RPMD rate theory in the adiabatic limit, and that of Wolynes theory in the nonadiabatic limit, and is therefore as accurate as any method could possibly be that attempts to generalize these methods to arbitrary electronic coupling strengths.

Experimental Demonstration of Dynamical Input Isolation in Nonadiabatically Modulated Photonic Cavities

Modulated optical cavities have been proposed and demonstrated for applications in communications, laser frequency stabilization, microwave-to-optical conversion and frequency comb generation. However, most studies are restricted to the adiabatic regime, where either the maximum excursion of the modulation or the modulation frequency itself is below the linewidth of the cavity. Here, using a fiber ring resonator with an embedded electro-optic phase modulator, we investigate the nonadiabatic regime. By strongly driving the modulator at frequencies that are significantly smaller than the free-spectral range of the ring resonator, but well beyond the linewidth of the resonator, we experimentally observe counterintuitive behavior predicted in a recent theoretical study by Minkov et al. [APL Photonics 2, 076101 (2017)], such as the complete suppression of drop-port transmission even when the input laser wavelength is on resonance with the optical cavity. This can be understood as dynamical isolation of the cavity from the input light. We also show qualitative differences in the steady-state responses of the system between the adiabatic and nonadiabatic limits. Our experiments probe a seldom explored regime of operation that is promising for applications in integrated photonic systems with current state-of-the-art technology.

Transitions from low-density state towards high-density state in stochastic bistable plasma-condensate systems

In this article we study transitions from low-density states towards high-density states in bistable plasma-condensate systems. We take into account an anisotropy in transference of adatoms between neighbour layers induced by the electric field near substrate. We derive the generalized one-layer model by assuming that the strength of the electric field is subjected to both periodic oscillations and multiplicative fluctuations. By studying the homogeneous system we discuss the corresponding mean passage time. In the limit of weak fluctuations, we show the optimization of the mean passage time with variation in the frequency of periodic driving in the non-adiabatic limit. Noise induced effects corresponding to asynchronization and acceleration in the transition dynamics are studied in detail.

Dynamics of polar polarizable rotors acted upon by unipolar electromagnetic pulses: From the sudden to the adiabatic regime.

We study, analytically as well as numerically, the dynamics that arises from the interaction of a polar polarizable rigid rotor with single unipolar electromagnetic pulses of varying length, Δτ, with respect to the rotational period of the rotor, τ r . In the sudden, non-adiabatic limit, Δτ ≪ τ r , we derive analytic expressions for the rotor's wavefunctions, kinetic energies, and field-free evolution of orientation and alignment. We verify the analytic results by solving the corresponding time-dependent Schrödinger equation numerically and extend the temporal range of the interactions considered all the way to the adiabatic limit, Δτ > τ r , where general analytic solutions beyond the field-free case are no longer available. The effects of the orienting and aligning interactions as well as of their combination on the post-pulse populations of the rotational states are visualized as functions of the orienting and aligning kick strengths in terms of population quilts. Quantum carpets that encapsulate the evolution of the rotational wavepackets provide the space-time portraits of the resulting dynamics. The population quilts and quantum carpets reveal that purely orienting, purely aligning, or even-break combined interactions each exhibit sui generis dynamics. In the intermediate temporal regime, we find that the wavepackets as functions of the orienting and aligning kick strengths show resonances that correspond to diminished kinetic energies at particular values of the pulse duration.

The Green’s function technique for numerical simulations of multichannel electron transfer reactions in electron-donor-acceptor complexes

A method for numerical solution of diffusion equations with delta-localized coupling terms is proposed and applied to the stochastic model of multichannel electron transfer (ET) reaction in the Debye polar solvent. The Green’s function for the model equations is calculated using the Laplace transform technique for the time-dependent reaction fluxes between the reactant and product states. Two computational schemes for ET simulations are suggested: (a) the particle-based Brownian algorithm, (b) the grid scheme, utilizing the probabilities of the diffusion-assisted electronic transitions. The suggested schemes are shown to be more efficient than the previously developed recrossing-algorithm (the RABS method) in the solvent-controlled ET regimes and for slow processes accompanied by rare reactive events. Test simulations with the QM2L code are carried out and demonstrate an accuracy of the method. The results of the simulations agree well with known analytical expressions for the rate of thermal ET and the quantum yield of nonequilibrium multichannel ET in different regimes from the nonadiabatic (the Fermi Golden Rule) limit to the solvent-controlled reactions.

Characteristics of chiral anomaly in view of various applications

In view of the recent applications of chiral anomaly to various fields beyond particle physics, we discuss some basic aspects of chiral anomaly which may help deepen our understanding of chiral anomaly in particle physics also. It is first shown that Berry's phase (and its generalization) for the Weyl model $H =v_{F} \vec{\sigma}\cdot \vec{p}(t)$ assumes a monopole form at the exact adiabatic limit but deviates from it off the adiabatic limit and vanishes in the high frequency limit of the Fourier transform of $\vec{p}(t)$ for bounded $|\vec{p}(t)|$. An effective action, which is consistent with the non-adiabatic limit of Berry's phase, combined with the Bjorken-Johnson-Low prescription gives normal equal-time space-time commutators and no chiral anomaly. In contrast, an effective action with a monopole at the origin of the momentum space, which describes Berry's phase in the precise adiabatic limit but fails off the adiabatic limit, gives anomalous space-time commutators and a covariant anomaly to the gauge current. We regard this anomaly as an artifact of the postulated monopole and not a consequence of Berry's phase. As for the recent application of the chiral anomaly to the description of effective Weyl fermions in condensed matter and nuclear physics, which is closely related to the formulation of lattice chiral fermions, we point out that the chiral anomaly for each species doubler separately vanishes for a finite lattice spacing, contrary to the common assumption. Instead a general form of pair creation associated with the spectral flow for the Dirac sea with finite depth takes place. This view is supported by the Ginsparg-Wilson fermion, which defines a single Weyl fermion without doublers on the lattice and gives a well-defined index (anomaly) even for a finite lattice spacing.