Nonequilibrium Excitation Research Articles

Ammonia pyrolysis oxidation excited by nanosecond pulsed discharge: Global/fluid models hybrid solution

The kinetic characteristics of plasma-assisted oxidative pyrolysis of ammonia are studied by using the global/fluid models hybrid solution method. Firstly, the stable products of plasma-assisted oxidative pyrolysis of ammonia are measured. The results show that the consumption of NH3/O2 and the production of N2/H2 change linearly with the increase of voltage, which indicates the decoupling of non-equilibrium molecular excitation and oxidative pyrolysis of ammonia at low temperatures. Secondly, the detailed reaction kinetics mechanism of ammonia oxidative pyrolysis stimulated by a nanosecond pulse voltage at low pressure and room temperature is established. Based on the reaction path analysis, the simplified mechanism is obtained. The detailed and simplified mechanism simulation results are compared with experimental data to verify the accuracy of the simplified mechanism. Finally, based on the simplified mechanism, the fluid model of ammonia oxidative pyrolysis stimulated by the nanosecond pulse plasma is established to study the pre-sheath/sheath behavior and the resultant consumption and formation of key species. The results show that the generation, development, and propagation of the pre-sheath have a great influence on the formation and consumption of species. The consumption of NH3 by the cathode pre-sheath is greater than that by the anode pre-sheath, but the opposite is true for OH and O(1S). However, within the sheath, almost all reactions do not occur. Further, by changing the parameters of nanosecond pulse power supply voltage, it is found that the electron number density, electron current density, and applied peak voltages are not the direct reasons for the structural changes of the sheath and pre-sheath. Furthermore, the discharge interval has little effect on the sheath structure and gas mixture breakdown. The research results of this paper not only help to understand the kinetic promotion of non-equilibrium excitation in the process of oxidative pyrolysis but also help to explore the influence of transport and chemical reaction kinetics on the oxidative pyrolysis of ammonia.

Collisional-radiative modeling of shock-heated nitrogen mixtures

A three-temperature collisional-radiative model for shock-heated nitrogen–argon mixtures is developed to facilitate the study of nonequilibrium electronic excitation and ionization behind strong shock waves. Model predictions accurately reproduce measurements of N2 dissociation for mixtures of 2%–10% N2 in argon, with some discrepancies observed for 20% N2 mixtures. Potential causes of the discrepancies are discussed. Net dissociation in mixtures containing 20% N2 is significantly impacted by the dissociation of N2(A), the first excited electronic state of N2, indicating that molecular electronic excitation can affect net dissociation in shock-heated nitrogen flows. The collisional-radiative model successfully predicts the three-stage behavior and induction time observed in concentration measurements of atomic nitrogen in its fourth excited state, the 3s4P level, behind reflected shocks. Mechanisms for the observed behavior are discussed, which deviate from those inferred using a simpler kinetic model. Excited state number density predictions are strongly influenced by the modeling of radiation self-absorption and the inclusion of the measured non-ideal pressure rise. At higher N2 concentrations, the measured data indicate increased efficiency of atomic nitrogen electronic excitation in collisions with N as compared to collisions with N2 and Ar. A global sensitivity analysis of the excited state predictions is then performed, identifying the processes in the kinetic model that most sensitively influence the predicted excited state time history and further clarifying the dominant mechanisms affecting the experimental observables.

Ignition enhancement and NOx formation of NH3/air mixtures by non-equilibrium plasma discharge

This work computationally studies plasma assisted low temperature NH3/air ignition and NOx formation in a repetitively-pulsed nanosecond discharge at atmospheric pressure by using an experimentally-validated plasma-combustion kinetic model. The results show that plasma discharge significantly enhances low temperature NH3 ignition. Compared with thermal ignition, the ignition delay time is shortened by 2–5 orders of magnitude due to the kinetic enhancement of excited species and radicals. The radicals (NH2, NH, H and O) produced through electron impact dissociation and quenching of electronically excited N2*, O(1D) and N(2D) promote OH production and further accelerate NH3 oxidation. The results show that there exists a non-monotonic dependence of ignition delay time on the reduced electric field strength. The optimum ignition enhancement is achieved at 250 Td at which the production of electronically excited species and radicals is most efficient. The vibrationally excited species produced at lower electric fields (<100 Td) are less effective in enhancing ignition because they only induce gas heating through the fast vibrational-translational relaxation by NH3 and H2O. At a higher electric field, although the efficient production of NH2, NH, H, O and OH by plasma creates new low temperature reaction pathways in enhancing low temperature NH3 ignition, the ignition is inhibited through NH + NO = N2O + H and chain-termination reaction NH2 + HO2 = NH3 + O2. The ignition delay times at different equivalence ratios show that the ignition enhancement by plasma is more effective at fuel-lean conditions due to the faster generation of N2(B), O(1D) and O from air, leading to accelerated NH3 oxidation via O(1D) + NH3→ NH2 + OH, NH3 + O = NH2 + OH and NH2 + O = NH + OH. The sensitivity analysis shows that the reactions involving O and O(1D) production are more effective on NH3 ignition enhancement than the fuel dissociation by electrons. Moreover, the ignition is also enhanced by NOx formation in plasma via reactions NH2 + NO = NNH + OH and NO + HO2 = NO2 + OH. This work advances the understanding of non-equilibrium excitation and NOx formation by plasma discharge on low temperature NH3 ignition.

Construction of sp2/sp3 Hybrid Carbon Thin Layers on Silicon Substrates Using Nonequilibrium Excitation Reaction Fields.

The authors have developed a crystal growth process that utilizes electron beams from field emission (FE) to grow materials bottom-up by a method other than the transfer of thermal energy. In this study, highly crystalline single-walled carbon nanotubes were used as a field emission electron source. Electron beams with high resolution energy emitted from the source were irradiated onto acetylene gas as a nonequilibrium reaction field to induce acetylene dissociation. The generated carbon ions were then irradiated onto a [100] silicon substrate, resulting in the irradiation of the silicon substrate surface with graphene. Moreover, the crystal growth of sp2/sp3 hybrid carbon thin layers, which is different from the crystal structures of graphite, diamond, and diamond-like carbon, proceeded on the surface of the silicon substrate. Carbon layers on periodic crystal structures whose growth depends at least on the morphology of the substrate are formed through bridging with the binding site of the substrate. The authors have succeeded in developing a nonthermal technique of crystal bridging between different elements. The substrate on which the carbon layer is formed is not limited to silicon; other substrates with various crystal structures and periodicities are expected to be used.

Nonequilibrium Fractional Josephson Effect.

Josephson tunnel junctions exhibit a supercurrent typically proportional to the sine of the superconducting phase difference ϕ. In general, a term proportional to cos(ϕ) is also present, alongside microscopic electronic retardation effects. We show that voltage pulses sharply varying in time prompt a significant impact of the cos(ϕ) term. Its interplay with the sin(ϕ) term results in a nonequilibrium fractional Josephson effect (NFJE) ∼sin(ϕ/2) in the presence of bound states close to zero frequency. Our microscopic analysis reveals that the interference of nonequilibrium virtual quasiparticle excitations is responsible for this phenomenon. We also analyze this phenomenon for topological Josephson junctions with Majorana bound states. Remarkably, the NFJE is independent of the ground state fermion parity unlike its equilibrium counterpart.

Energy relaxation in (La0.6Pr0.4)0.7Ca0.3MnO3 films across the metal-insulator transition

The colossal magnetoresistive manganite ${({\mathrm{La}}_{0.6}{\mathrm{Pr}}_{0.4})}_{0.7}{\mathrm{Ca}}_{0.3}{\mathrm{MnO}}_{3}$ (LPCMO) undergoes a ferromagnetic (FM) metal to paramagnetic insulator phase transition at around 195 K, which develops via an intermediate polaronic state strongly susceptible to external magnetic fields. Transient reflectivity studies of LPCMO on timescales from sub-picoseconds to nanoseconds reveal that the overall system dynamics are strongly influenced by the phase transition with a sharp and strong decrease in the relaxation time while crossing from the ferromagnetic metallic phase into the paramagnetic insulating phase. We show that the long relaxation times of the reflectivity after nonequilibrium excitation within the FM phase are caused by the slow recovery of the ordered FM state after laser-induced demagnetization. Control of the nonequilibrium dynamics close to the phase transition is demonstrated by applying moderate magnetic fields below 1 T.

Electronic heat generation in semiconductors: Non-equilibrium excitation and evolution of zone-edge phonons via electron–phonon scattering in photo-excited germanium

We investigate experimentally and using first-principles theory the generation of phonons and the relaxation of carriers on picosecond timescales across the Brillouin zone of photo-excited Ge by inter-valley electron–phonon scattering. The phonons generated are typical of those generated in semiconductor devices, contributing to the accumulation of heat within the material. We simulate the time-evolution of phonon populations, based on first-principles band structure and electron–phonon and phonon–phonon matrix elements, and compare them to data from time-resolved x-ray diffuse scattering experiments, performed at the Linac Coherent Light Source x-ray free-electron laser facility, following photo-excitation by a 50 fs near-infrared optical pulse. We show that the intensity of the non-thermal x-ray diffuse scattering signal, which is observed to grow substantially near the L-point of the Brillouin zone over 3–5 ps, is due to phonons generated by scattering of carriers between the Δ and L valleys. These phonons have low group velocities, resulting in a heat bottleneck. With the inclusion of phonon decay through 3-phonon processes, the simulations also account for other non-thermal features observed in the x-ray diffuse scattering intensity, which are due to anharmonic phonon–phonon scattering of the phonons initially generated by electron–phonon scattering.

State-to-state vibrational kinetics of diatomic molecules in laser-induced ignition of a syngas-air mixture: Modeling study

A thermally nonequilibrium model was created to describe the processes occurring in a syngas-air mixture when exposed to intense CO laser radiation. The model consistently describes the reactions of syngas oxidation in air and the state-to-state vibrational kinetics of CO, N2, O2, H2, and OH molecules and also takes into account the nonequilibrium vibrational excitation of polyatomic molecules in the mode approximation. Using the constructed model, the possibility of laser-induced ignition of syngas in air was analyzed. Special attention was paid to the influence of the efficiency of vibrational energy of CO molecules in overcoming the energy barriers of reactions on the simulation results. For the key reactions involving CO molecules, the values of the coefficients of vibrational energy usage were estimated employing the method of classical single-trajectory calculations. It was shown that these coefficients are the critical parameters determining the possibility of using the CO laser radiation to accelerate the ignition of syngas. In addition, we have shown that in the problem considered, because of the strong nonequilibrium excitation of CO vibrations, it is extremely important to take into account the deviation of the vibrational distribution functions of molecules from the Boltzmann one, which requires the use of a state-to-state model of vibrational nonequilibrium. The inaccuracy in calculating the laser-induced ignition time of syngas in air by means of a mode model can reach an order of magnitude.

Long-Range Nonequilibrium Coherent Tunneling Induced by Fractional Vibronic Resonances.

We study the influence of a linear energy bias on a nonequilibrium excitation on a chain of molecules coupled to local vibrations (a tilted Holstein model) using both a random-walk rate kernel theory and a nonperturbative, massively parallelized adaptive-basis algorithm. We uncover structured and discrete vibronic resonance behavior fundamentally different from both linear response theory and homogeneous polaron dynamics. Remarkably, resonance between the phonon energy ℏω and the bias δϵ occurs not only at integer but also fractional ratios δϵ/(ℏω) = m/n, which effect long-range n-bond m-phonon tunneling. These observations are reproduced in a model calculation of a recently demonstrated Cy3 system, and the effect of dipole-dipole-type non-nearest-neighbor coupling and vibrationally relaxed initial states is also considered. Potential applications range from molecular electronics to optical lattices and artificial light harvesting via vibronic engineering of coherent quantum transport.

Modeling of the effects of non-equilibrium excitation and electrode geometry on H2/air ignition in a nanosecond plasma discharge

This work presents the results of two-dimensional modeling of the effects of non-equilibrium excitation and electrode geometry on H2/air ignition in a nanosecond plasma discharge. A multiscale adaptive reduced chemistry solver for plasma assisted combustion (MARCS-PAC) based on PASSKEy discharge modeling package and compressible multi-component reactive flow solver ASURF+ is developed and validated. This model is applied to simulate the impact of non-equilibrium plasma excitation and electrode geometry and heat loss on the dynamics of the discharge from streamer to spark and ignition kernel development in a H2/air mixture with a pair of cylindrical electrodes. The results show that the plasma-generated species (N2(A), N2(B), N2(a′), N2(C), O(1D), O and H) in the spark and afterglow significantly accelerate the ignition kernel development. The increase of discharge voltage at the same total discharge energy promotes the non-equilibrium active species production. It is found that the production of electronically excited species at higher reduced electric field strength is more efficient in enhancing ignition in comparison to the vibrational excitation and heating. Moreover, the 2D simulation clearly reveals that the electric field and active species distribution are highly non-uniform. The streamers are initiated at the sharp outer edges of the negative and positive electrodes by a strong electric field while the electric field is much weaker at the centerline of the electrodes. Furthermore, the simulations reveal that the ignition enhancement is sensitive to the variation of electrode shape, diameter, and gap size due to the changes of electric field distribution and location of streamer formation. A cylindrical electrode produces a larger discharge volume and ignition kernel than the parabolic and spherical electrodes, when the discharge is localized near the axis of the gap. It is found that there is a non-monotonic dependence of ignition kernel size on the electrode diameter and inter-electrode distance. The increase of electrode diameter and gap size above the optimal conditions leads to the reduction of ignition kernel volume, due to the decrease of active species concentration and gas temperature. At a larger electrode surface area and electrode diameter as well as smaller electrode gap size, the heat loss to electrode plays a greater role in reducing the ignition kernel size and slowing ignition kernel development. This work provides insights and guidance to understand the kinetic enhancement of non-equilibrium plasma and the effects of electrode geometries on ignition for the optimization ignitors in advanced engines.

Interaction-driven dynamical quantum phase transitions in a strongly correlated bosonic system

We study dynamical quantum phase transitions (DQPTs) in the extended Bose-Hubbard model after a sudden quench of the nearest-neighbor interaction strength. Using the time-dependent density matrix renormalization group, we demonstrate that interaction-driven DQPTs can appear after quenches between two topologically trivial insulating phases---a phenomenon that has so far only been studied between gapped and gapless phases. These DQPTs occur when the interaction strength crosses a certain threshold value that does not coincide with the equilibrium phase boundaries, which is in contrast to quenches that involve a change of topology. In order to elucidate the nonequilibrium excitations during the time evolution, we define a new set of string and parity order parameters. We find a close connection between DQPTs and these newly defined order parameters for both types of quenches. In the interaction-driven case, the order parameter exhibits a singularity at the time of the DQPT only when the quench parameter is close to the threshold value. Finally, the timescales of DQPTs are scrutinized and different kinds of power laws are revealed for the topological and interaction-driven cases.

Engineering high-coherence superconducting qubits

Advances in materials science and engineering have played a central role in the development of classical computers and will undoubtedly be critical in propelling the maturation of quantum information technologies. In approaches to quantum computation based on superconducting circuits, as one goes from bulk materials to functional devices, amorphous films and non-equilibrium excitations — electronic and phononic — are introduced, leading to dissipation and fluctuations that limit the computational power of state-of-the-art qubits and processors. In this Review, the major sources of decoherence in superconducting qubits are identified through an exploration of seminal qubit and resonator experiments. The proposed microscopic mechanisms associated with these imperfections are summarized, and directions for future research are discussed. The trade-offs between simple qubit primitives based on a single Josephson tunnel junction and more complex designs that use additional circuit elements, or new junction modalities, to reduce sensitivity to local noise sources are discussed, particularly in the context of materials optimization strategies for each architecture. Superconducting qubits hold great promise for quantum computing, and recently there have been dramatic improvements in both coherence times and the power of quantum processors. This Review explores how the path forward involves balancing circuit complexity and materials perfection, eliminating defects while designing qubits with engineered noise resilience.

Structural instability of transition metals upon ultrafast laser irradiation

Precision in laser material structuring is critically defined by the energy flow during the irradiation process, particularly in ultrafast regimes. Alternative to thermal evolutions, nonequilibrium electronic excitation can exercise a direct influence on the atomic bonding delivering a potentially rapid destructuring process. In this context, the atomic disordering of transition metals (Cr, Ni, and Ti) induced by nonequilibrium electronic excitation typical for ultrafast laser processing is studied with an emphasis on the role of the $d$-band filling and crystalline structure. The density functional theory is used to obtain, from first principles, structural stability criteria and nonthermal disordering pathways on timescales shorter than picosecond electron-phonon dynamics. We show that the hot electrons distort charge distribution in the cold crystalline arrangement and increase the entropy of the system, thus driving the mechanical expansion. The calculated nonequilibrium free-energy potentials indicate that a solid destabilization is possible when electron temperature reaches a universal value of around 2 eV for all considered metals. Under a uniaxial lattice relaxation expected in the laser ablation of surface layers, the charge redistribution and loss of lattice stability is shown to be oriented along specific crystal directions. Moreover, we show that the interatomic potential destabilization is energetically more favorable for Ni than for Cr and Ti. Lattice dynamics is affected by space-charge redistribution induced by Fermi smearing associated with anisotropic expansion due to electron pressure gradients. This ultrafast destructuring mechanism is shown to be a general feature of partially filled $d$-band transition metals.

Nonequilibrium optical response of a one-dimensional Mott insulator

We define, compute and analyze the nonequilibrium differential optical conductivity of the one-dimensional extended Hubbard model at half-filling after applying a pump pulse, using the time-dependent density matrix renormalization group method. The melting of the Mott insulator is accompanied by a suppression of the local magnetic moment and ensuing photogeneration of doublon-holon pairs. The differential optical conductivity reveals $(i)$ mid-gap states related to parity-forbidden optical states, and $(ii)$ strong renormalization and hybridization of the excitonic resonance and the absorption band, yielding a Fano resonance. We offer evidence and interpret such a resonance as a signature of nonequilibrium optical excitations resembling excitonic strings, (bi)excitons, and unbound doublon-holon pairs, depending on the magnitude of the intersite Coulomb repulsion. We discuss our results in the context of pump and probe spectroscopy experiments on organic Mott insulators.

Nonthermal Crystalline Forming of Zinc Oxide Nanoparticles by Non-Equilibrium Excitation Reaction Field of Field Emission Electron

Nonthermal Crystalline Forming of Zinc Oxide Nanoparticles by Non-Equilibrium Excitation Reaction Field of Field Emission Electron

Atomic-Level, Energy-Conversion Heat Transfer

Abstract Heat is stored in quanta of kinetic and potential energies in matter. The temperature represents the equilibrium and excited occupation (boson) of these energy conditions. Temporal and spatial temperature variations and heat transfer are associated with the kinetics of these equilibrium excitations. During energy-conversion (between electron and phonon systems), the occupancies deviate from equilibria, while holding atomic-scale, inelastic spectral energy transfer kinetics. Heat transfer physics reaches nonequilibrium energy excitations and kinetics among the principal carriers, phonon, electron (and holes and ions), fluid particle, and photon. This allows atomic-level tailoring of energetic materials and energy-conversion processes and their efficiencies. For example, modern thermal-electric harvesters have transformed broad-spectrum, high-entropy heat into a narrow spectrum of low-entropy emissions to efficiently generate thermal electricity. Phonoelectricity, in contrast, intervenes before a low-entropy population of nonequilibrium optical phonons becomes a high-entropy heat. In particular, the suggested phonovoltaic cell generates phonoelectricity by employing the nonequilibrium, low-entropy, and elevated temperature optical-phonon produced population—for example, by relaxing electrons, excited by an electric field. A phonovoltaic material has an ultranarrow electronic bandgap, such that the hot optical-phonon population can relax by producing electron-hole pairs (and power) instead of multiple acoustic phonons (and entropy). Examples of these quanta and spectral heat transfer are reviewed, contemplating a prospect for education and research in this field.

Nanometer-Thick Crystalline Carbon Films Having a Spinel Structure Grown on ZnO Substrates: Implications for New Ceramic–Carbon Composition

I developed a bottom-up process of crystal growth using a field emission (FE) electron beam without transfer of heat energy. In this study, highly crystalline single-walled carbon nanotubes were used as the FE electron source. Acetylene was irradiated with an electron beam of high-resolution energy emitted from the electron source. Then, zinc oxide (ZnO) was irradiated with the carbon-based ions dissociated from the acetylene and electron beam, which formed a nonequilibrium excitation reaction field. As a result, a crystalline carbon thin film with a spinel-like structure different from the structures of graphite and diamond was grown on the ZnO surface. It is considered that the carbon film can be formed on substrates with a periodic crystal structure, not only ZnO. I confirmed that a carbon film with a periodic crystal structure independent of the crystal structure of the underlying substrate was grown, which bridged with the substrate. Thus, I have established a technique of crystal bridging between a ceramic and carbon for the first time to the best of our knowledge.

Relaxation dynamics of the optically driven nonequilibrium states in the electron- and hole-doped topological-insulator materials (Bi1−xSbx)2Te3

We report on time-resolved mid-infrared-pump terahertz-transmission-probe studies of the topological-insulator materials $(Bi_{1-x}Sb_{x})_{2}Te_{3}$, in which by varying x charge carriers are chemically tuned to be of n-type or p-type. Relaxation dynamics is found to be different in various aspects for transitions below or above the bandgap, which are selectively excited by changing the pump-pulse energy. For the below-bandgap excitation, an exponential decay of the pump-probe signals is observed, which exhibits linear dependence on the pump-pulse fluence. In contrast, the relaxation dynamics for the above-bandgap excitation is characterized by a compressed exponential decay and nonlinear fluence dependence at high pump flunences, which reflects interaction of the excited nonequilibrium states.

Kibble-Zurek scaling in quantum speed limits for shortcuts to adiabaticity

Geometric quantum speed limits quantify the trade-off between the rate with which quantum states can change and the resources that are expended during the evolution. Counterdiabatic driving is a unique tool from shortcuts to adiabaticity to speed up quantum dynamics while completely suppressing nonequilibrium excitations. We show that the quantum speed limit for counterdiabatically driven systems undergoing quantum phase transitions fully encodes the Kibble-Zurek mechanism by correctly predicting the transition from adiabatic to impulse regimes. Our findings are demonstrated for three scenarios, namely the transverse field Ising, the Landau-Zener, and the Lipkin-Meshkov-Glick models.

An In-situ and Direct Confirmation of Super-Planckian Thermal Radiation Emitted From a Metallic Photonic-Crystal at Optical Wavelengths

Planck’s law predicts the distribution of radiation energy, color and intensity, emitted from a hot object at thermal equilibrium. The Law also sets the upper limit of radiation intensity, the blackbody limit. Recent experiments reveal that micro-structured tungsten can exhibit significant deviation from the blackbody spectrum. However, whether thermal radiation with weak non-equilibrium pumping can exceed the blackbody limit in the far field remains un-answered experimentally. Here, we compare thermal radiation from a micro-cavity/tungsten photonic crystal (W-PC) and a blackbody, which are both measured from the same sample and also in-situ. We show that thermal radiation can exceed the blackbody limit by >8 times at λ = 1.7 μm resonant wavelength in the far-field. Our observation is consistent with a recent calculation by Wang and John performed for a 2D W-PC filament. This finding is attributed to non-equilibrium excitation of localized surface plasmon resonances coupled to nonlinear oscillators and the propagation of the electromagnetic waves through non-linear Bloch waves of the W-PC structure. This discovery could help create super-intense narrow band thermal light sources and even an infrared emitter with a laser-like input-output characteristic.