Nonequilibrium Dynamics of Electron Emission from Cold and Hot Graphene under Proton Irradiation.

Characteristic properties of secondary electrons emitted from irradiated two-dimensional materials arise from multi-length and multi-time-scale relaxation processes that connect the initial nonequilibrium excited electron distribution with their eventual emission. To understand these processes, which are critical for using secondary electrons as high-resolution thermalization probes, we combine first-principles real-time electron dynamics with irradiation experiments. Our data for cold and hot proton-irradiated graphene show signatures of kinetic and potential emission and generally good agreement for electron yields between experiment and theory. The duration of the emission pulse is about 1.5 fs, which indicates high time resolution when used as a probe. Our newly developed method to predict kinetic energy spectra shows good agreement with electron and ion irradiation experiments and prior models. We find that the lattice temperature significantly increases secondary electron emission, whereas electron temperature has a negligible effect.

Finite Temperature String with Order Parameter as Collective Variables for Molecular Crystal: A Case of Polymorphic Transformation of TNT under External Electric Field.

An external electric field is an effective tool to induce the polymorphic transformation of molecular crystals, which is important practically in the chemical, material, and energy storage industries. However, the understanding of this mechanism is poor at the molecular level. In this work, two types of order parameters (OPs) were constructed for the molecular crystal based on the intermolecular distance, bond orientation, and molecular orientation. Using the K-means clustering algorithm for the sampling of OPs based on the Euclidean distance and density weight, the polymorphic transformation of TNT was investigated using a finite temperature string (FTS) under external electric fields. The potential of mean force (PMF) was obtained, and the essence of the polymorphic transformation between o-TNT and m-TNT was revealed, which verified the effectiveness of the FTS method based on K-means clustering to OPs. The differences in PMFs between the o-TNT and transition state were decreased under external electric fields in comparison with those in no field. The fields parallel to the c-axis obviously affected the difference in PMF, and the relationship between the changes in PMFs and field strengths was found. Although the external electric field did not promote the convergence, the time of the polymorphic transformation was reduced under the external electric field in comparison to its absence. Moreover, under the external electric field, the polymorphic transformation from o-TNT to m-TNT occurred while that from m-TNT to o-TNT was prevented, which was explained by the dipole moment of molecule, relative permittivity, chemical potential difference, nucleation work and nucleation rate. This confirmed that the polymorphic transformation orientation of the molecular crystal could be controlled by the external electric field. This work provides an effective way to explore the polymorphic transformation of the molecular crystals at a molecular level, and it is useful to control the production process and improve the performance of energetic materials by using the external electric fields.

Experimental and Theoretical Investigation of External Electric-Field-Induced Crystallization of TKX-50 from Solution by Finite-Temperature String with Order Parameters as Collective Variables for Ionic Crystals.

External electric fields are an effective tool to induce phase transformations. The crystallization of ionic crystals from solution is a common phase transformation. However, understanding of mechanisms is poor at the molecular level. In this work, we carried out an experimental and theoretical investigation of the external electric-field-induced crystallization of TKX-50 from saturated formic acid solution by finite-temperature string (FTS) with order parameters (OPs) as collective variables for ionic crystals. The minimum-free-energy path was sketched by the string method in collective variables. The results show that the K-means clustering algorithm based on Euclidean distance and density weights can be used for enhanced sampling of the OPs in external electric-field-induced crystallization of ionic crystal from solution, which improves the conventional FTS. The crystallization from solution is a process of surface-mediated nucleation. The external electric field can accelerate the evolution of the string and decrease the difference in the potential of mean forces between the crystal and the transition state. Due to the significant change in OPs induced by the external electric field in nucleation, the crystalline quality was enhanced, which explains the experimental results that the external electric field enhanced the density, detonation velocity, and detonation pressure of TKX-50. This work provides an effective way to explore the crystallization of ionic crystals from solution at the molecular level, and it is useful for improving the properties of ionic crystal explosives by using external electric fields.

Phase transitions and the birth of early universe particle physics.

This paper provides a conceptual history of the development of early universe particle physics in the 1970s, focusing on the development of more sophisticated tools for constructing gauge-theories at finite-temperature. I start with a focus on early investigations into spontaneous symmetry restoration, and continue through the development of functional methods up to equilibrium finite-temperature field theory. I argue that the early universe provides an ideal setting for integrated modelling of thermal, gravitational, and particle physics effects due to its relative simplicity. I further argue that the development of finite-temperature field theory played an important secondary role in the rise of the effective field theory worldview, and investigate the status of the analogies between phase transitions in particle physics and condensed matter physics. I find that the division into "formal" versus "physical" analogies is too coarse-grained to understand the important physical developments at play.

Magic Numbers and Mixing Degree in Many-Fermion Systems.

We consider an N fermion system at low temperature T in which we encounter special particle number values Nm exhibiting special traits. These values arise when focusing attention upon the degree of mixture (DM) of the pertinent quantum states. Given the coupling constant of the Hamiltonian, the DMs stay constant for all N-values but experience sudden jumps at the Nm. For a quantum state described by the matrix ρ, its purity is expressed by Trρ2 and then the degree of mixture is given by 1-Trρ2, a quantity that coincides with the entropy Sq for q=2. Thus, Tsallis entropy of index two faithfully represents the degree of mixing of a state, that is, it measures the extent to which the state departs from maximal purity. Macroscopic manifestations of the degree of mixing can be observed through various physical quantities. Our present study is closely related to properties of many-fermion systems that are usually manipulated at zero temperature. Here, we wish to study the subject at finite temperature. The Gibbs ensemble is appealed to. Some interesting insights are thereby gained.

Demonstration of Nanosecond Operation in Stochastic Magnetic Tunnel Junctions.

Magnetic tunnel junctions operating in the superparamagnetic regime are promising devices in the field of probabilistic computing, which is suitable for applications like high-dimensional optimization or sampling problems. Further, random number generation is of interest in the field of cryptography. For such applications, a device's uncorrelated fluctuation time-scale can determine the effective system speed. It has been theoretically proposed that a magnetic tunnel junction designed to have only easy-plane anisotropy provides fluctuation rates determined by its easy-plane anisotropy field and can perform on a nanosecond or faster time-scale as measured by its magnetoresistance's autocorrelation in time. Here, we provide experimental evidence of nanosecond scale fluctuations in a circular-shaped easy-plane magnetic tunnel junction, consistent with finite-temperature coupled macrospin simulation results and prior theoretical expectations. We further assess the degree of stochasticity of such a signal.

Atomistic theory of thermally activated magnetization processes in Nd2Fe14B permanent magnet.

To study the temperature dependence of magnetic properties of permanent magnets, methods of treating the thermal fluctuation causing the thermal activation phenomena must be established. To study finite-temperature properties quantitatively, we need atomistic energy information to calculate the canonical distribution. In the present review, we report our recent studies on the thermal properties of the Nd2Fe14B magnet and the methods of studying them. We first propose an atomistic Hamiltonian and show various thermodynamic properties, for example, the temperature dependences of the magnetization showing a spin reorientation transition, the magnetic anisotropy energy, the domain wall profiles, the anisotropy of the exchange stiffness constant, and the spectrum of ferromagnetic resonance. The effects of the dipole-dipole interaction (DDI) in large grains are also presented. In addition to these equilibrium properties, the temperature dependence of the coercivity of a single grain was studied using the stochastic Landau-Lifshitz-Gilbert equation and also by the analysis of the free energy landscape, which was obtained by Monte Carlo simulation. The upper limit of coercivity at room temperature was found to be about 3 T at room temperature. The coercivity of a polycrystalline magnet, that is, an ensemble of interactinve grains, is expected to be reduced further by the effects of the grain boundary phase, which is also studied. Surface nucleation is a key ingredient in the domain wall depinning process. Finally, we study the effect of DDI among grains and also discuss the distribution of properties of grains from the viewpoint of first-order reversal curve.

Comment on "The Nature of Chalcogen-Bonding-Type Tellurium-Nitrogen Interactions": Fixing the Description of Finite-Temperature Effects Restores the Agreement Between Experiment and Theory.

Mitzel and co-workers recently presented an intriguing molecule displaying a tellurium-nitrogen interaction. Structural data obtained in the solid and in gas phase indicated a large increase of the Te-N equilibrium distance re from 2.64 to 2.92 Å, respectively. Although some DFT calculations appear to support the large re in gas phase, we argue that the lions share of the increase is due to an incomplete description of finite-temperature effects in the back-corrected experimental data. This hypothesis is based on high-level coupled-cluster (CC) and periodic DFT calculations, which consistently point towards a much smaller re in the isolated molecule. Further support comes through MD simulations with a tuned GFN2-xTB Hamiltonian: Calibrated against a CC reference, these show a six-times larger influence of temperature than with the originally used GFN1-xTB. Taking this into account, the back-corrected re in gas phase becomes 2.67±0.08 Å, in good agreement with high-level CC theory and most DFT methods.

Unbinding free energy of acetylcholinesterase bound oxime drugs along the gorge pathway from metadynamics-umbrella sampling investigation.

Because of the pivotal role that the nerve enzyme, acetylcholinesterase plays in terminating nerve impulses at cholinergic synapses. Its active site, located deep inside a 20 Å gorge, is a vulnerable target of the lethal organophosphorus compounds. Potent reactivators of the intoxicated enzyme are nucleophiles, such as bispyridinium oxime that binds to the peripheral anionic site and the active site of the enzyme through suitable cation-π interactions. Atomic scale molecular dynamics and free energy calculations in explicit water are used to study unbinding pathways of two oxime drugs (Ortho-7 and Obidoxime) from the gorge of the enzyme. The role of enzyme-drug cation-π interactions are explored with the metadynamics simulation. The metadynamics discovered potential of mean force (PMF) of the unbinding events is refined by the umbrella sampling (US) corrections. The bidimensional free energy landscape of the metadynamics runs are further subjected to finite temperature string analysis to obtain the transition tube connecting the minima and bottlenecks of the unbinding pathway. The PMF is also obtained from US simulations using the biasing potential constructed from the transition tube and are found to be consistent with the metadynamics-US corrected results. Although experimental structural data clearly shows analogous coordination of the two drugs inside the gorge in the bound state, the PMF of the drug trafficking along the gorge pathway point, within an equilibrium free energy context, to a multistep process that differs from one another. Routes, milestones and subtlety toward the unbinding pathway of the two oximes at finite temperature are identified.

Combining complementary ligands into one framework for the construction of a ferromagnetically coupled [Mn(III)12] wheel.

Phenolic oxime and diethanolamine moieties have been combined into one organic framework, resulting in the formation of a novel ligand type that can be employed to construct a rare and unusual dodecametallic Mn wheel, within which nearest neighbours are coupled ferromagnetically.

Theoretical scheme for finite-temperature dynamics of Kitaev's spin liquids.

In this article, we review the theoretical formulation of finite temperature dynamics of Kitaev's spin liquid. We present the exact analytical solution of the dynamical spin correlation function at the integrable limit of Kitaev's model, on the basis of (2018Phys. Rev. B98220404). By combining the analytical solution with the equilibrium classical Monte-Carlo scheme, we construct a formulation to access the finite temperature dynamics of Kitaev's spin liquid exactly, with a reasonable amount of computational cost. This formulation is based on the real-time representation, which enables us to directly access the experimental observables defined in real frequency, without analytical continuation. The real-time scheme is essential to capturing the resonant features of the spectrum accurately, which occurs e.g. in the chiral spin liquid phase with isolated Majorana zero modes. Accordingly, this scheme provides an effective approach to address the nature of fractional excitations in Kitaev's spin liquid. As an application, we address the detection of zero mode around the site vacancy through the local resonant spectrum and discuss how the character of Kitaev's spin liquid emerges in its dynamical signature.

Predicted stable high-pressure phases of copper-nitrogen compounds.

The nitrogen-rich compounds are promising candidates for high-energy-density applications, owing to the large difference in the bonding energy between triple and single/double nitrogen bonds. The exploration of stable copper-nitrogen (Cu-N) compounds with high-energy-density has been challenging for a long time. Recently, through a combination of high temperatures and pressures, a new copper diazenide compound (P63/mmc-CuN2) has been synthesized (Binnset al2019J. Phys. Chem. Lett.101109-1114). But the pressure-composition phase diagram of Cu-N compounds at different temperatures is still highly unclear. Here, by combining first-principles calculations with crystal structure prediction method, the Cu-N compounds with different stoichiometric ratios were searched within the pressure range of 0-150 GPa. Four Cu-N compounds are predicted to be thermodynamically stable at high pressures,Pnnm-CuN2, two CuN3compounds with theP-1 space group (named as I-CuN3and II-CuN3) andP21/m-CuN5containing cyclo-N5-. Finite temperature effects (vibrational energies) play a key role in stabilizing experimentally synthesizedP63/mmc-CuN2at ∼55 GPa, compared to our predictedPnnm-CuN2. These new Cu-N compounds show great promise for potential applications as high-energy-density materials with the energy densities of 1.57-2.74 kJ g-1.

Thermodynamics of spin-1/2 Kagomé Heisenberg antiferromagnet: algebraic paramagnetic liquid and finite-temperature phase diagram.

Quantum fluctuations from frustration can trigger quantum spin liquids (QSLs) at zero temperature. However, it is unclear how thermal fluctuations affect a QSL. We employ state-of-the-art tensor network-based methods to explore the ground state and thermodynamic properties of the spin-1/2 kagomé Heisenberg antiferromagnet (KHA). Its ground state is shown to be consistent with a gapless QSL by observing the absence of zero-magnetization plateau as well as the algebraic behaviors of susceptibility and specific heat at low temperatures, respectively. We show that there exists an algebraic paramagnetic liquid (APL) that possesses both the paramagnetic properties and the algebraic behaviors inherited from the QSL. The APL is induced under the interplay between quantum fluctuations from geometrical frustration and thermal fluctuations. By studying the temperature-dependent behaviors of specific heat and magnetic susceptibility, a finite-temperature phase diagram in a magnetic field is suggested, where various phases are identified. This present study gains useful insight into the thermodynamic properties of the spin-1/2 KHA with or without a magnetic field and is helpful for relevant experimental studies.

Designing Two-Dimensional Dirac Heterointerfaces of Few-Layer Graphene and Tetradymite-Type Sb2Te3 for Thermoelectric Applications.

Despite the ubiquitous nature of the Peltier effect in low-dimensional thermoelectric devices, the influence of finite temperature on the electronic structure and transport in the Dirac heterointerfaces of the few-layer graphene and layered tetradymite, Sb2Te3 (which coincidently have excellent thermoelectric properties) are not well understood. In this work, using the first-principles density-functional theory calculations, we investigate the detailed atomic and electronic structure of these Dirac heterointerfaces of graphene and Sb2Te3 and further re-examine the effect of finite temperature on the electronic band structures using a phenomenological temperature-broadening model based on Fermi-Dirac statistics. We then proceed to understand the underlying charge redistribution process in this Dirac heterointerfaces and through solving the Boltzmann transport equation, we present the theoretical evidence of electron-hole asymmetry in its electrical conductivity as a consequence of this charge redistribution mechanism. We finally propose that the hexagonal-stacked Dirac heterointerfaces are useful as efficient p-n junction building blocks in the next-generation thermoelectric devices where the electron-hole asymmetry promotes the thermoelectric transport by "hot" excited charge carriers.

Existence of hyperbolic calorons.

Recent work of Harland shows that the SO(3)-symmetric, dimensionally reduced, charge-N self-dual Yang-Mills calorons on the hyperbolic space [Formula: see text] may be obtained through constructing N-vortex solutions of an Abelian Higgs model as in the study of Witten on multiple instantons. In this paper, we establish the existence of such minimal action charge-N calorons by constructing arbitrarily prescribed N-vortex solutions of the Witten type equations.