Nonadiabatic Approach Research Articles

Investigating electron-induced dissociation dynamics in the organometallic precursor Fe(CO)5: a nonadiabatic molecular dynamics approach

This research employs excited states molecular dynamics simulations to explore the electron-induced dissociation behavior of Fe(CO)5 molecules, with the specific focus on electronic excitation. The study initiates with the detailed analysis of the molecule’s stable ground state structure. Subsequent simulations reveal distinctive dissociation patterns in various bonds, particularly noting the rapid dissociation of bonds between Fe and C1, Fe and C2, while those with Fe and C3 oscillate without complete dissociation. Emphasizing the influence of the transition from the highest occupied molecular orbital to the lowest unoccupied molecular orbital on reactivity, the investigation sheds light on the charge transfer phenomenon during dissociation through Bader analysis. Insights into transitions between excited and ground states are derived from the time evolution of the Kohn–Sham orbital. This study significantly contributes to understanding intricate dissociation mechanisms under electronic excitation, especially in molecules like Fe(CO)5 characterized by complex chemical bonds. Beyond theoretical exploration, the research holds practical significance for applications in nanomaterials, such as focused electron beam-induced deposition and the fabrication of nanoscale structures, enriching our comprehension of electronic-excitation-induced dissociation and advancing both theoretical understanding and practical applications in this field.

Nonadiabatic molecular dynamics with subsystem density functional theory: application to crystalline pentacene

In this work, we report the development and assessment of the nonadiabatic molecular dynamics approach with the electronic structure calculations based on the linearly scaling subsystem density functional method. The approach is implemented in an open-source embedded Quantum Espresso/Libra software specially designed for nonadiabatic dynamics simulations in extended systems. As proof of the applicability of this method to large condensed-matter systems, we examine the dynamics of nonradiative relaxation of excess excitation energy in pentacene crystals with the simulation supercells containing more than 600 atoms. We find that increased structural disorder observed in larger supercell models induces larger nonadiabatic couplings of electronic states and accelerates the relaxation dynamics of excited states. We conduct a comparative analysis of several quantum-classical trajectory surface hopping schemes, including two new methods proposed in this work (revised decoherence-induced surface hopping and instantaneous decoherence at frustrated hops). Most of the tested schemes suggest fast energy relaxation occurring with the timescales in the 0.7–2.0 ps range, but they significantly overestimate the ground state recovery rates. Only the modified simplified decay of mixing approach yields a notably slower relaxation timescales of 8–14 ps, with a significantly inhibited ground state recovery.

Prolonged Exciton Lifetime Is Achieved in Porphyrin Nanoring by Template Engineering: A Nonadiabatic Tight Binding Approach.

Porphyrin nanoring has been attracting immense attention due to its light harvesting capacity and potential applications in optical, catalysis, sensor, and electronic devices. We demonstrate by nonadiabatic quantum dynamics simulations that the photovoltaic efficiency can be enhanced by template engineering. Altering the hexadentate template (T6) with two tridentate templates (2T3) within the porphyrin ring (P6) cavity accelerated the electron transfer twice and suppressed the electron-hole recombination by nearly three times. The atomistic tight-binding simulation rationalized the dynamics by different localizations of charge of the band edge states, changes in nonadiabatic coupling, alteration in quantum coherence, and involvement of diverse electron-phonon vibrational modes. Further 2T3 templates more strongly hold the P6 ring than T6, reducing the structural fluctuation. As a result, the nonadiabatic coupling becomes weaker and suppresses the carrier recombination. Current atomistic simulation presents a template engineering strategy to enhance the exciton lifetime along with ultrafast charge separation, crucial factors for photovoltaic applications.

Real-Time Ab Initio Investigation on Hot Electron Relaxation Dynamics in Silicon.

The relaxation of hot electrons in semiconductors is pivotal for both energy harvesting processes and optoelectronics. Utilizing a self-developed non-adiabatic molecular dynamics simulation approach in the momentum space (NAMD_k), we have examined the dynamics of hot electrons in silicon. Whether excited from the Γ or L point, the relaxation dynamics exhibit two distinct stages. Initially, within 100 fs, electrons scatter with phonons throughout the Brillouin zone. Subsequently, over a few picoseconds, they further relax toward the conduction band minimum as a whole. This picture of hot electron relaxation is highly consistent with the quasi-equilibrium hot electron ensemble (HEE) concept. Throughout the hot electron relaxation process, energy transfer to phonons is efficient, leading to time-dependent phonon excitation, which is thoroughly analyzed. This investigation provides a novel perspective on hot electron relaxation in silicon, which holds substantive implications for the realm of photovoltaic and optoelectronic device applications.

Formation of Ar2+ ions in cold argon plasmas through the ternary recombination mechanism

A general scheme for calculating ternary recombination rate constants of atomic species based on a hybrid quantum–classical nonadiabatic dynamics approach is presented and applied to the specific case of the ternary recombination of atomic ions of argon in cold argon plasmas. Rate constants are reported for both fine-structure states of the Ar+ ion, 2P3/2 and 2P1/2 , T = 300 K, and for selected values of the reduced electric field. A thorough comparison with the literature data available for T = 300 K and a couple of close temperatures is performed with a favorable agreement achieved. It is shown that the excited Ar+(2P1/2) ions may contribute to the formation of dimer ions, Ar2+ , as efficiently as the ground-state ions, Ar+(2P3/2) , due to fast internal conversion of the electronic energy, which takes place in ternary collision complexes, Ar+/Ar/Ar .

Influence of donor or acceptor presence on excitation states in molecular chains: Nonadiabatic polaron approach.

In this paper, we considered a molecular structure that consists of a molecular chain and an additional molecule (donor or acceptor) that can inject (or remove) single excitation (vibron, electron, etc.) onto the molecular chain. We assumed that the excitation forms a self-trapped state due to the interaction with mechanical oscillations of the chain structure elements. We analyzed the energy spectra of the excitation and showed that its state (when it migrates to the molecular chain) has the properties of the nonadiabatic polaron state. The conditions under which the excitation can migrate from one subsystem to another one were considered. It was shown that the presence of a "donor" molecule cannot significantly change the properties of the excitation located on the molecular chain. At the same time, the molecular chain can affect the position of the energy level of the excitation localized on the donor subsystem. Indirectly, this can influence the process of excitation migration from one subsystem to another one. The influence of the basic energy parameters of the system and the environment temperature on this process are discussed. The entire system was assumed to be in thermal equilibrium with the environment.

Nonadiabatic Field on Quantum Phase Space: A Century after Ehrenfest.

Nonadiabatic transition dynamics lies at the core of many electron/hole transfer, photoactivated, and vacuum field-coupled processes. About a century after Ehrenfest proposed "Phasenraum" and the Ehrenfest theorem, we report a conceptually novel trajectory-based nonadiabatic dynamics approach, nonadiabatic field (NAF), based on a generalized exact coordinate-momentum phase space formulation of quantum mechanics. It does not employ the conventional Born-Oppenheimer or Ehrenfest trajectory in the nonadiabatic coupling region. Instead, in NAF the equations of motion of the independent trajectory involve a nonadiabatic nuclear force term in addition to an adiabatic nuclear force term of a single electronic state. A few benchmark tests for gas phase and condensed phase systems indicate that NAF offers a practical tool to capture the correct correlation of electronic and nuclear dynamics for processes where the states remain coupled all the time as well as for the asymptotic region where the coupling of electronic states vanishes.

Nonadiabatic molecular dynamics study on effect of Ge/Sn alloy on hot carrier relaxation of CsPbBr<sub>3</sub> perovskite

Perovskite solar cells have been a prominent focus in the field of photovoltaics in recent decades, owing to their exceptional performance: easy synthesis, and cost-effectiveness. The all-inorganic cesium-based perovskite CsPbBr<sub>3</sub>, known for its remarkable thermal stability, has become a star material in the field of optoelectronics due to its outstanding luminescent properties. Despite the high efficiency of lead-based perovskite solar cells, the toxicity associated with lead and the poor long-term stability of these devices remain significant barriers to their large-scale commercialization. As is well known, non-radiative electron-hole recombination significantly shortens the carrier lifetime, acting as a primary pathway for excited state charge to loss energy. This phenomenon directly affects the photovoltaic conversion efficiency and charge transfer performance of perovskite materials. Therefore, maximizing the reduction of non-radiative recombination energy loss in perovskite solar cells has become a crucial research focus. In this study, a systematic exploration is conducted by using a non-adiabatic molecular dynamics approach combined with time-dependent density functional theory to investigate the excited-state carrier dynamics of CsPbBr<sub>3</sub> and its alloyed structures, CsPb<sub>0.75</sub>Ge<sub>0.25</sub>Br<sub>3</sub> and CsPb<sub>0.5</sub>Ge<sub>0.25</sub>Sn<sub>0.25</sub>Br<sub>3</sub>. The study comprehensively analyzes the non-radiative electron-hole recombination scenarios and the mechanisms for reducing charge energy loss based on crystal structure, electronic properties, and excited-state properties. The research findings reveal that alloying with Sn/Ge can reduce the bandgap, increase non-adiabatic coupling, and shorten the decoherence time. The interplay of reduced quantum decoherence, smaller bandgap, and larger non-adiabatic coupling effectively decelerates the electron-hole recombination process. Consequently, the carrier lifetime of the CsPb<sub>0.75</sub>Ge<sub>0.25</sub>Br<sub>3</sub> system extends by 1.6 times. Moreover, under the joint influence of Sn/Ge, the carrier lifetime of the CsPb<sub>0.5</sub>Ge<sub>0.25</sub>Sn<sub>0.25</sub>Br<sub>3</sub> system extends by 4.2 times compared with those of the original system. The overall sequence follows CsPb<sub>0.5</sub>Ge<sub>0.25</sub>Sn<sub>0.25</sub>Br<sub>3</sub> > CsPb<sub>0.75</sub>Ge<sub>0.25</sub>Br<sub>3</sub> > CsPbBr<sub>3</sub>. This study underscores the significant influence of binary alloying of B-site metal cations (in the perovskite structure <i>ABX</i><sub>3</sub>, where B-site refers to the metal cation) on the non-radiative electron-hole recombination of CsPbBr<sub>3</sub>.This research presents an effective alloying scheme that substantially prolongs the carrier lifetime of perovskites, offering a rational approach to optimizing solar cell performance. It lays the groundwork for the future design of perovskite solar cell materials.

Effect of electron-electron interaction on polarization process of exciton and biexciton in conjugated polymers

Abstract By using the one-dimensional tight-binding model modified to include electron-electric field interaction and electron-electron interaction, we theoretically explore the polarization process of exciton and biexciton in cis-polyacetylene. The dynamical simulation is performed by adopting the non-adiabatic evolution approach. The results show that under the effect of moderate electric field, when the strength of electron-electron interaction is weak, the singlet exciton is stable but its polarization presents obvious oscillation. With the enhancement of interaction, it is dissociated into polaron pair, the spin-flip of which could be observed through modulating the interaction strength. For the triplet exciton, the strong electron-electron interaction restrains its normal polarization, but it is still stable. In case of biexciton, the strong electron-electron interaction not only dissociate it, but also flip its charge distribution. We also calculate the yield of the possible states formed after the dissociation of exciton and biexciton.

Quantum dynamics simulations of the 2D spectroscopy for exciton polaritons.

We develop an accurate and numerically efficient non-adiabatic path-integral approach to simulate the non-linear spectroscopy of exciton-polariton systems. This approach is based on the partial linearized density matrix approach to model the exciton dynamics with explicit propagation of the phonon bath environment, combined with a stochastic Lindblad dynamics approach to model the cavity loss dynamics. Through simulating both linear and polariton two-dimensional electronic spectra, we systematically investigate how light-matter coupling strength and cavity loss rate influence the optical response signal. Our results confirm the polaron decoupling effect, which is the reduced exciton-phonon coupling among polariton states due to the strong light-matter interactions. We further demonstrate that the polariton coherence time can be significantly prolonged compared to the electronic coherence outside the cavity.

Neutral-to-ionic photoinduced phase transition of tetrathiafulvalene-p-chloranil by electronic and vibrational excitation: A real-time nuclear-electronic dynamics simulation study.

Tetrathiafulvalene-p-chloranil exhibits photoinduced phase transition (PIPT) between neutral (N) and ionic (I) phases, in which the constituent molecules are approximately charge-neutral and ionic, respectively. In addition to visible-light irradiation, which can induce both N → I and I → N PIPTs, infrared irradiation has been reported to induce the N → I PIPT. These results suggest that N → I and I → N PIPTs can be driven by electronic excitation, and the I → N PIPT can also be driven by vibrational excitation. However, the feasibility of the N → I PIPT using vibrational excitation remains an open question. In this study, we address this issue by simulating the PIPT processes using a nonadiabatic molecular dynamics approach combined with real-time electron dynamics at the level of a semiempirical quantum chemical model, density-functional tight binding. The results show the importance of vibronic interactions in the PIPT processes, thereby suggesting the possibility of N → I PIPT by vibrational excitations with infrared irradiation.

A priori and a posteriori analysis of flamelet modeling for large-eddy simulations of a non-adiabatic backward-facing step

A lean premixed ethylene–air flame in a backstep configuration is simulated on multiple grids using both direct numerical simulations (DNS) with reduced order kinetic mechanism and large eddy simulations (LES) with flamelet-based thermochemistry. The configuration includes preheated reactants and a recirculation zone that provides radicals and high temperature gases to stabilize the flame. Heat losses are present due to the proximity of cooled walls. The reacting flow obtained from DNS at different resolutions is first analyzed to investigate the property of heat transfer within the recirculation region. LES based on adiabatic flamelets with a correction of the heat capacity is then tested, and its ability to account for heat losses is compared to results obtained using a three-dimensional non-adiabatic flamelet approach. Mean fields and subgrid properties are compared to those obtained from DNS to assess the capability of the LES models. The results show that the non-adiabatic flamelet approach can predict recirculation region and temperature fields with good accuracy. The model with heat capacity correction is able to effectively correct the heat capacity behavior as observed by a priori comparisons. However, in the a posteriori context, it is observed to overestimate the temperature field, although the correct size of the recirculation region is predicted. The combined a priori and a posteriori analyses on the same configuration and at different mesh resolutions allow for a precise separation of modeling effects due to heat transfer at the wall and combustion closure, thus providing indications on the LES performance in the context of flamelets.

A mapping approach to surface hopping.

We present a nonadiabatic classical-trajectory approach that offers the best of both worlds between fewest-switches surface hopping (FSSH) and quasiclassical mapping dynamics. This mapping approach to surface hopping (MASH) propagates the nuclei on the active adiabatic potential-energy surface, such as in FSSH. However, unlike in FSSH, transitions between active surfaces are deterministic and occur when the electronic mapping variables evolve between specified regions of the electronic phase space. This guarantees internal consistency between the active surface and the electronic degrees of freedom throughout the dynamics. MASH is rigorously derivable from exact quantum mechanics as a limit of the quantum-classical Liouville equation (QCLE), leading to a unique prescription for momentum rescaling and frustrated hops. Hence, a quantum-jump procedure can, in principle, be used to systematically converge the accuracy of the results to that of the QCLE. This jump procedure also provides a rigorous framework for deriving approximate decoherence corrections similar to those proposed for FSSH. We apply MASH to simulate the nonadiabatic dynamics in various model systems and show that it consistently produces more accurate results than FSSH at a comparable computational cost.

The Resonance Raman Spectrum of Cytosine in Water: Analysis of the Effect of Specific Solute-Solvent Interactions and Non-Adiabatic Couplings.

In this contribution, we report a computational study of the vibrational Resonance Raman (vRR) spectra of cytosine in water, on the grounds of potential energy surfaces (PES) computed by time-dependent density functional theory (TD-DFT) and CAM-B3LYP and PBE0 functionals. Cytosine is interesting because it is characterized by several close-lying and coupled electronic states, challenging the approach commonly used to compute the vRR for systems where the excitation frequency is in quasi-resonance with a single state. We adopt two recently developed time-dependent approaches, based either on quantum dynamical numerical propagations of vibronic wavepackets on coupled PES or on analytical correlation functions for cases in which inter-state couplings were neglected. In this way, we compute the vRR spectra, considering the quasi-resonance with the eight lowest-energy excited states, disentangling the role of their inter-state couplings from the mere interference of their different contributions to the transition polarizability. We show that these effects are only moderate in the excitation energy range explored by experiments, where the spectral patterns can be rationalized from the simple analysis of displacements of the equilibrium positions along the different states. Conversely, at higher energies, interference and inter-state couplings play a major role, and the adoption of a fully non-adiabatic approach is strongly recommended. We also investigate the effect of specific solute-solvent interactions on the vRR spectra, by considering a cluster of cytosine, hydrogen-bonded by six water molecules, and embedded in a polarizable continuum. We show that their inclusion remarkably improves the agreement with the experiments, mainly altering the composition of the normal modes, in terms of internal valence coordinates. We also document cases, mostly for low-frequency modes, in which a cluster model is not sufficient, and more elaborate mixed quantum classical approaches, in explicit solvent models, need to be applied.

Modeling of Sandia Flame D with the non-adiabatic chemistry tabulation approach: the effects of different laminar flames on NO X prediction.

The effects of different one-dimensional laminar flames on the prediction of nitrogen oxide (NO X ) emission in Sandia Flame D are numerically investigated using a flamelet method in the present work. In addition to the basic control variables of the mixture fraction and the reaction progress variable for chemistry tabulation in this combustion model, two additional variables of mixture fraction variance and enthalpy loss are added to the control variable space to improve prediction accuracy of the NO X pollutant. The former variable of mixture fraction variance is used for the presumed probability density function integration, and the latter takes into account the non-adiabatic effect. Two flamelet libraries are generated based on the one-dimensional unstretched premixed flame and the one-dimensional counterflow diffusion flame, respectively. An additional transport equation for the mass fraction of nitrogen oxide (NO) is solved for improving prediction accuracy. The unsteady Reynolds-averaged Navier-Stokes (URANS) simulation results are compared and analyzed with experimental data. The simulation results show dependence on the type of laminar flame. In the four-dimensional control variable space, the results with steady unstretched premixed flame indicate great agreement on the predictions of temperature and NO field. The computational method proposed in the present work sheds light on the high-precision combustion numerical simulation of NO X emission.

Photodetachment band of the fluorenyl anion: a theoretical rationalization.

In order to rationalize the experimental photodetachment spectra of the fluorenyl anion, nuclear dynamics studies are performed using adiabatic and non-adiabatic quantum chemistry approaches. The adiabatic dynamics calculations are performed on the basis of FC_Class and Poisson simulations. The outcomes from these simulations explain most of the experimental observations. Later, time-independent non-adiabatic nuclear dynamics calculations using vibronic coupling theory (VCT) are performed to elucidate the origin of a few vibrational peaks that do not appear in the results from adiabatic dynamics calculations. In addition, time-dependent non-adiabatic nuclear dynamics calculations using the same VCT approach are performed to rationalize the lifetime of the excited state of the fluorenyl anion. It is found that the photodetachment band obtained from the non-adiabatic simulations is in better agreement with the experimental findings.

A Comprehensive Approach to Exciton Delocalization and Energy Transfer.

Electrostatic intermolecular interactions lie at the heart of both the Förster model for resonance energy transfer (RET) and the exciton model for energy delocalization. In the Förster theory of RET, the excitation energy incoherently flows from the energy donor to a weakly coupled energy acceptor. The exciton model describes instead the energy delocalization in aggregates of identical (or nearly so) molecules. Here, we introduce a model that brings together molecular aggregates and RET. We will consider a couple of molecules, each described in terms of two diabatic electronic states, coupled to an effective molecular vibration. Electrostatic intermolecular interactions drive energy fluxes between the molecules, that, depending on model parameters, can be described as RET or energy delocalization. At variance with the standard Förster model for RET and of the exciton model for aggregates, our approach applies both in the weak and in the strong coupling regimes and fully accounts for the quantum nature of molecular vibrations in a nonadiabatic approach. Coupling the system to a thermal bath, we follow RET and energy delocalization in real time and simulate time-resolved emission spectra.

Coronal seismology by slow waves in non-adiabatic conditions

Slow magnetoacoustic waves represent an important tool for probing the solar coronal plasma. The majority of seismological methods with slow waves are based on a weakly non-adiabatic approach, which assumes the coronal energy transport has only weak effects on the wave dynamics. Despite it significantly simplifies the application of coronal seismology by slow waves, this assumption omits a number of important and confidently observed effects and thus puts strong limitations on the reliability of seismological estimations. We quantitatively assess the applicability of the weak thermal conduction theory to coronal seismology by slow waves. We numerically model the linear standing slow wave in a 1D coronal loop, with field-aligned thermal conduction κ‖ as a free parameter and no restrictions on its efficiency. The time variations of the perturbed plasma parameters, obtained numerically with full conductivity, are treated as potential observables and analysed with the standard data processing techniques. The slow wave oscillation period is found to increase with κ‖ by about 30%, indicating the corresponding modification in the effective wave speed, which is missing from the weak conduction theory. Phase shifts between plasma temperature and density perturbations are found to be well consistent with the approximate weakly conductive solution for all considered values of κ‖. In contrast, the comparison of the numerically obtained ratio of temperature and density perturbation amplitudes with the weak theory revealed relative errors up to 30–40%. We use these parameters to measure the effective adiabatic index of the coronal plasma directly as the ratio of the effective slow wave speed to the standard sound speed and in the polytropic assumption, which is found to be justified in a weakly conductive regime only, with relative errors up to 14% otherwise. The damping of the initial perturbation is found to be of a non-exponential form during the first cycle of oscillation, which could be considered as an indirect signature of entropy waves in the corona, also not described by weak conduction theory. The performed analysis and obtained results offer a more robust scheme of coronal seismology by slow waves, with reasonable simplifications and without the loss of accuracy.

Quasi-diabatic propagation scheme for simulating polariton chemistry.

We generalize the quasi-diabatic (QD) propagation scheme to simulate the non-adiabatic polariton dynamics in molecule-cavity hybrid systems. The adiabatic-Fock states, which are the tensor product states of the adiabatic electronic states of the molecule and photon Fock states, are used as the locally well-defined diabatic states for the dynamics propagation. These locally well-defined diabatic states allow using any diabatic quantum dynamics methods for dynamics propagation, and the definition of these states will be updated at every nuclear time step. We use several recently developed non-adiabatic mapping approaches as the diabatic dynamics methods to simulate polariton quantum dynamics in a Shin-Metiu model coupled to an optical cavity. The results obtained from the mapping approaches provide very accurate population dynamics compared to the numerically exact method and outperform the widely used mixed quantum-classical approaches, such as the Ehrenfest dynamics and the fewest switches surface hopping approach. We envision that the generalized QD scheme developed in this work will provide a powerful tool to perform the non-adiabatic polariton simulations by allowing a direct interface between the diabatic dynamics methods and ab initio polariton information.

Effects of triaxiality and residual np interaction in the proton emission from Ho140

We present a detailed theoretical investigation of proton emission from $^{140}\mathrm{Ho}$ within the nonadiabatic quasiparticle approach. The calculated proton emission half-life reproduces well the measured data. The importance of triaxiality and of the residual $np$ interaction are studied. The ground state spin and parity of $^{139}\mathrm{Dy}$ (daughter) and $^{140}\mathrm{Ho}$ (parent) are ascertained unambiguously as $7/{2}^{+}$ and ${3}^{\ensuremath{-}}$, respectively, by analyzing the rotational energies, half-lives, and branching ratios.