Nonadiabatic Effects Research Articles

Complex Berry phase dynamics in PT -symmetric coupled waveguides

We show that the analogue of the geometric phase for non-Hermitian coupled waveguides with PT-symmetry and at least one periodically varying parameter can be purely imaginary, and will consequently result in the manifestation of an instability in the system. The instability peaks seen in the spectrum of the system's eigenstates after evolution along the waveguides can be directly mapped to the spectrum of the derivative of the geometric function. The instabilities are magnified as the exceptional point of the system is approached, and non-adiabatic effects begin to appear. As the system cannot evolve adiabatically in the vicinity of the exceptional point, PT-symmetry will be observed breaking earlier than theoretically predicted.

Nonadiabatic relativistic correction in H2 , D2 , and HD

We calculate the nonadiabatic relativistic correction to rovibrational energy levels of H$_2$, D$_2$, and HD molecules using the nonadiabatic perturbation theory. This approach allows one to obtain nonadiabatic corrections to all the molecular levels with the help of a single effective potential. The obtained results are in very good agreement with the previous direct calculation of nonadiabatic relativistic effects for dissociation energies and resolve the reported discrepancies of theoretical predictions with recent experimental results.

Coulomb potential effects in strong-field atomic ionization under elliptical polarization

We experimentally and theoretically investigate strong-field ionization of noble-gas atoms in elliptically polarized laser fields at 2000 nm. The ellipticity dependence of the ion yields has been measured at a series of intensities and compared to various theoretical model predictions [i.e., the Ammosov-Delone-Krainov (ADK), strong-field approximation (SFA), and Coulomb-Volkov distorted-wave approximation (CVA) models]. The SFA and ADK calculations match each other, which alludes to the negligible contribution of nonadiabatic effect. In the meantime, they both deviate significantly from the measurements. On the other hand, the good agreement between CVA calculations and measurements reveals the salient role played by the Coulomb potential in atomic ionization. The Coulomb potential effect is further confirmed by comparison of CVA calculations and measurements at 800 nm. Our work demonstrates the significant Coulomb potential effect on the ionization yields, the experimental evidence of which has rarely been documented.

Mechanism of the O2 (1 Δg ) generation from the Cl2 /H2 O2 basic aqueous solution explored by the combined ab initio calculation and nonadiabatic dynamics simulation.

In the present work, mechanism of the O2 (1 Δg ) generation from the reaction of the dissolved Cl2 with H2 O2 in basic aqueous solution has been explored by the combined ab initio calculation and nonadiabatic dynamics simulation, together with different solvent models. Three possible pathways have been determined for the O2 (1 Δg ) generation, but two of them are sequentially downhill processes until formation of the OOCl- complex with water, which are of high exothermic character. Once the complex is formed, singlet molecular oxygen is easily generated by its decomposition along the singlet-state pathway. However, triplet molecular oxygen of O2 ( ) can be produced with considerable probability through nonadiabatic intersystem crossing in the 1 Δg / intersection region. It has been found that the coupled solvent, heavy-atom, and nonadiabatic effects have an important influence on the quantum yield of the O2 (1 Δg ) generation. © 2018 Wiley Periodicals, Inc.

Fast adiabatic evolution by oscillating initial Hamiltonians

We propose a method to produce fast transitionless dynamics for finite-dimensional quantum systems without requiring additional Hamiltonian components not included in the initial control setup, remaining close to the true adiabatic path at all times. The strategy is based on the introduction of an effective counterdiabatic scheme: a correcting Hamiltonian is constructed which approximatively cancels nonadiabatic effects, inducing an evolution tracking the adiabatic states closely. This can be absorbed into the initial Hamiltonian by adding a fast oscillation in the control parameters. We show that a consistent speedup can be achieved without requiring strong control Hamiltonians, using it both as a stand-alone shortcut-to-adiabaticity and as a weak correcting field. A number of examples are treated, dealing with quantum state transfer in avoided-crossing problems and entanglement creation.

Probing Nonadiabatic Effects in Low-Energy C(3 P j) + H2 Collisions.

Nonadiabatic effects are of fundamental interest in collision dynamics. In particular, inelastic collisions between open-shell atoms and molecules, such as the collisional excitation of C(3 P j) by H2, are governed by nonadiabatic and spin-orbit couplings that are the sole responsible of collisional energy transfer. Here, we study collisions between carbon in its ground state C(3 P j=0) and molecular hydrogen (H2) at low collision energies that result in spin-orbit excitation to C(3 P j=1) and C(3 P j=2). State-to-state integral cross sections are obtained experimentally from crossed-beam experiments with a source of almostpure beam of C(3 P j=0) and theoretically from highly accurate quantum calculations. We observe very good agreement between experimental and theoretical data that demonstrates our ability to model nonadiabatic dynamics. New rate coefficients at temperatures relevant to astrochemical modeling are also provided. They should lead to an increase of the abundance of atomic C(3 P) derived from the observations of interstellar clouds and a decrease of the efficiency of the cooling of the interstellar gas due to carbon atoms.

Adiabatic and Nonadiabatic Effects in the Transition States of State to State Autoionization Processes.

The energy distribution of electrons, emitted from collisions between Ne^{*}(^{3}P_{2,0}) and Kr(^{1}S_{0}), have been measured under high resolution conditions in a crossed molecular beam apparatus containing a hemispherical electron analyzer as detector. The experimental results provide new insights on the electronic adiabatic and nonadiabatic effects in the stereodynamics of state to state atomic and molecular collisions, controlling relevant properties of the transition state of autoionization processes. In particular, while the adiabatic effects determine sequence, energy, and symmetry of quantum states accessible both to reagents and products, the nonadiabatic effects trigger the passage from entrance to exit channels.

Real-Time Observation of Molecular Spinning with Angular High-Harmonic Spectroscopy.

We demonstrate an angular high-harmonic spectroscopy method to probe the spinning dynamics of a molecular rotation wave packet in real time. With the excitation of two time-delayed, polarization-skewed pump pulses, the molecular ensemble is impulsively kicked to rotate unidirectionally, which is subsequently irradiated by another delayed probe pulse for high-order harmonic generation (HHG). The spatiotemporal evolution of the molecular rotation wave packet is visualized from the time-dependent angular distributions of the HHG yields and frequency shift measured at various polarization directions and time delays of the probe pulse. The observed frequency shift in HHG is demonstrated to arise from the nonadiabatic effect induced by molecular spinning. Different from the previous spectroscopic and Coulomb explosion imaging techniques, the angular high-harmonic spectroscopy method can reveal additionally the electronic structure and multiple orbitals of the sampled molecule. All the experimental findings are well reproduced by numerical simulations. Further extension of this method would provide a powerful tool for probing complex polyatomic molecules with HHG spectroscopy.

Reaction-Induced Excitations and Their Effect on Surface Chemistry

Despite intensive study of reactions on metals, it is unclear whether electronic excitations play an important role. Here, we show that nonadiabatic effects do indeed play a significant role in N2 ...

Conical Intersections Induced by Quantum Light: Field-Dressed Spectra from the Weak to the Ultrastrong Coupling Regimes.

In classical laser fields with frequencies resonant with the electronic excitation in molecules, it is by now known that conical intersections are induced by the field and are called light-induced conical intersections (LICIs). As optical cavities have become accessible, the question arises whether their quantized modes could also lead to the appearance of LICIs. A theoretical framework is formulated for the investigation of LICIs of diatomics in such quantum light. The eigenvalue spectrum of the dressed states in the cavity is studied, putting particular emphasis on the investigation of absorption spectra of the Na2 molecule, that is, on the transitions between dressed states, measured by employing a weak probe pulse. The dependence of the spectra on the light-matter coupling strength in the cavity and on the frequency of the cavity mode is studied in detail. The computations demonstrate strong nonadiabatic effects caused by the appearing LICI.

Multiexcitons in flexible Rydberg aggregates

Flexible Rydberg aggregates, assemblies of few Rydberg atoms coherently sharing electronic excitations while undergoing directed atomic motion, show great promise as quantum simulation platform for nuclear motional dynamics in molecules or quantum energy transport. Here we study additional features that are enabled by the presence of more than a single electronic excitation, thus considering multi-exciton states. We describe cases where these can be decomposed into underlying single exciton states and then present dynamical scenarios with atomic motion that illustrate exciton-exciton collisions, exciton routing, and strong non-adiabatic effects in simple one-dimensional settings.

High-fidelity non-adiabatic cutting and stitching of a spin chain via local control

We propose and analyze, focusing on non-adiabatic effects, a technique of manipulating quantum spin systems based on local ‘cutting’ and ‘stitching’ of the Heisenberg exchange coupling between the spins. This first operation is cutting of a bond separating a single spin from a linear chain, or of two neighboring bonds for a ring-shaped array of spins. We show that the disconnected spin can be in the ground state with a high-fidelity even after a non-adiabatic process. Next, we consider inverse operation of stitching these bonds to increase the system size. We show that the optimal control algorithm can be found by using common numerical procedures with a simple two-parametric control function able to produce a high-fidelity cutting and stitching. These results can be applied for manipulating ensembles of quantum dots, considered as prospective elements for quantum information technologies, and for design of machines based on quantum thermodynamics.

Anomalous Phonon Lifetime Shortening in Paramagnetic CrN Caused by Spin-Lattice Coupling: A Combined Spin and AbInitio Molecular Dynamics Study.

We study the mutual coupling of spin fluctuations and lattice vibrations in paramagnetic CrN by combining atomistic spin dynamics and abinitio molecular dynamics. The two degrees of freedom are dynamically coupled, leading to nonadiabatic effects. Those effects suppress the phonon lifetimes at low temperature compared to an adiabatic approach. The dynamic coupling identified here provides an explanation for the experimentally observed unexpected temperature dependence of the thermal conductivity of magnetic semiconductors above the magnetic ordering temperature.

Dependence of Rydberg-state creation by strong-field ionization on laser intensity

We investigate numerically and analytically the intensity dependence of the fraction of electrons that end up in a Rydberg state after strong-field ionization with linearly polarized light. We find that including the intensity dependent distribution of ionization times and non-adiabatic effects leads to a better understanding of experimental results. Furthermore, we observe using Classical Trajectory Monte Carlo simulations that the intensity dependence of the Rydberg yield changes with wavelength and that the previously observed power-law dependence breaks down at longer wavelengths. Our work suggests that Rydberg yield measurements can be used as an independent test for non-adiabaticity in strong field ionization.

Treatment of Herzberg-Teller and non-Condon effects in optical spectra with Hierarchical Equations of Motion

We derive a Hierarchical Equations of Motion (HEOM) description of nonadiabatic Herzberg-Teller type coupling effects and of non-Condon effects in a system of electronic transitions interacting with intra- and inter-molecular vibrational modes. We point out analogies between the auxiliary density operators (ADOs) of the hierarchy and the terms arising from explicit description of the vibrational modes in the Hamiltonian. In comparison with the standard formulation of HEOM, our equations contain additional connections between ADOs in the hierarchy scheme, which account for the dependence of the nonadiabatic coupling elements on the vibrational coordinates. We compare absorption spectra calculated with our HEOM methodology and with explicit treatment of vibrational DOF for a dimer system in the strong resonance coupling regime. Furthermore, we show that for sufficiently strong excitonic coupling, the corresponding effects in linear absorption spectra of vibronic dimers can be captured very well by the concept of effective Huang-Rhys factors.

Nonadiabatic Relativistic Correction to the Dissociation Energy of H_{2}, D_{2}, and HD.

The relativistic correction to the dissociation energy of H_{2}, D_{2}, and HD molecules has been accurately calculated without expansion in the small electron-nucleus mass ratio. The obtained results indicate the significance of nonadiabatic effects and resolve the discrepancy of theoretical predictions with recent experimental values for H_{2} and D_{2}. While the theoretical accuracy is now significantly improved and is higher than the experimental one, we observe about 3σ discrepancy for the dissociation energy of HD, which requires further investigation.

Photochemistry of CF3Cl: Quenching of Charged Fragments Is Caused by Nonadiabatic Effects.

For the first time, high-level multireference electronic structure calculations have been performed to study the photochemistry of CF3Cl, allowing a comprehensive interpretation and assignment of experimental data concerning fluorescence, ion-pair formation, and generation of CF3 fragments in several electronic states. All studied dissociation channels correlate either with Cl or Cl- in the ground state. On the other hand, a CF3 fragment can be generated either in the ground or excited state. A rationalization for the nonadiabatic relaxation of CF3Cl, including the formation of an (n4s) stable state and internal conversion at multiple-state intersections, has been provided. Our results explain the anomalous quenching of a charged fragment after low-energy excitation, a fact experimentally observed by separate groups. We show that the CF3+···Cl- ion pair undergoes an internal conversion to the ground state, producing neutral CF3 and Cl fragments. The results also allow understanding as to why CF3Cl is usually a nonemitting species and how UV emission could be induced.

Attosecond Pump-Probe Spectroscopy of Charge Dynamics in Tryptophan.

Attosecond pump-probe experiments performed in small molecules have allowed tracking charge dynamics in the natural time scale of electron motion. That this is also possible in biologically relevant molecules is still a matter of debate, because the large number of available nuclear degrees of freedom might destroy the coherent charge dynamics induced by the attosecond pulse. Here we investigate extreme ultraviolet-induced charge dynamics in the amino acid tryptophan. We find that, although nuclear motion and nonadiabatic effects introduce some decoherence in the moving electron wave packet, these do not significantly modify the coherence induced by the attosecond pulse during the early stages of the dynamics, at least for molecules in their equilibrium geometry. Our conclusions are based on elaborate theoretical calculations and the experimental observation of sub-4 fs dynamics, which can only be reasonably assigned to electronic motion. Hence, attosecond pump-probe spectroscopy appears as a promising approach to induce and image charge dynamics in complex molecules.

Photodetachment spectroscopy of carbon doped anionic boron cluster, [formula omitted]: A theoretical study

The photodetachment spectroscopy of CB9- is theoretically studied in this paper. Extensive ab initio quantum chemistry calculations are carried out to construct the potential energy surfaces of the electronic ground and excited states of CB9. With the aid of these calculated adiabatic electronic energies, a vibronic coupling model is developed in a diabatic electronic basis and in terms of normal coordinates of vibrational modes following the standard vibronic coupling theory originally developed by Köppel et al. (1984). Employing the developed diabatic electronic model, first principles nuclear dynamics study is carried out to calculate the vibronic structure of photodetachment bands of CB9-. A systematic study is performed to elucidate the impact of electronic nonadiabatic effects on the photodetachment bands. The vibronic structure of the latter is assigned in terms of excitation of vibrational modes and the results are compared with the experimental findings. The internal conversion dynamics through conical intersections of electronic states is examined by analyzing the time-dependent electronic populations. The theoretical results are found to be in good agreement with the experimental data. The detailed theoretical study carried out here unambiguously supports the prediction of the global minimum structure of CB9-.

Reduced sensitivity of the (d,p) cross sections to the deuteron model beyond the adiabatic approximation

It has recently been reported [Phys. Rev. Lett. 117, 162502 (2016)] that (d, p) cross sections can be very sensitive to the n-p interactions used in the adiabatic treatment of deuteron breakup with nonlocal nucleon-target optical potentials. To understand to what extent this sensitivity could originate in the inaccuracy of the adiabatic approximation we have developed a leading-order local- equivalent continuum-discretized coupled-channel model that accounts for non-adiabatic effects in the presence of nonlocality of nucleon optical potentials. We have applied our model to the astro- physically relevant reaction $^{26m}$Al$(d, p) ^{27}$Al using two different n-p potentials associated with the lowest and the highest n-p kinetic energy in the short-range region of their interaction, respectively. Our calculations reveal a significant reduction of the sensitivity to the high n-p momenta thus confirming that it is mostly associated with theoretical uncertainties of the adiabatic approximation itself. The non-adiabatic effects in the presence of nonlocality were found to be stronger than those in the case of the local optical potentials. These results argue for extending the analysis of the $(d, p)$ reactions, measured for spectroscopic studies, beyond the adiabatic approximation.