Ab initio nonadiabatic molecular dynamics study on spin–orbit coupling induced spin dynamics in ferromagnetic metals

Understanding the photoexcitation induced spin dynamics in ferromagnetic metals is important for the design of photo-controlled ultrafast spintronic device.In this work,by the ab initio nonadiabatic molecular dynamics simulation,we have studied the spin dynamics induced by spin–orbit coupling(SOC)in Co and Fe using both spin-diabatic and spin-adiabatic representations.In Co system,it is found that the Fermi surface(E_(F))is predominantly contributed by the spin-minority states.The SOC induced spin flip will occur for the photo-excited spin-majority electrons as they relax to the E_(F),and the spin-minority electrons tend to relax to the EFwith the same spin through the electron–phonon coupling(EPC).The reduction of spin-majority electrons and the increase of spin-minority electrons lead to demagnetization of Co within100 fs.By contrast,in Fe system,the E_(F) is dominated by the spin-majority states.In this case,the SOC induced spin flip occurs for the photo-excited spin-minority electrons,which leads to a magnetization enhancement.If we move the E_(F) of Fe to higher energy by 0.6eV,the E_(F) will be contributed by the spin-minority states and the demagnetization will be observed again.This work provides a new perspective for understanding the SOC induced spin dynamics mechanism in magnetic metal systems.

Exact solution of slow quench dynamics and nonadiabatic characterization of topological phases

Previous studies have shown that the bulk topology of single-particle systems can be captured by the band inversion surface or by the spin inversion surface emerging on the time-averaged spin polarization.Most of the studies,however,are based on the single-particle picture even though the systems are fermionic and multi-bands.Here,we study the slow quench dynamics of topological systems with all the valence bands fully occupied,and show that the concepts of band inversion surface and spin inversion surface are still valid.More importantly,the many-particle nonadiabatic quench dynamics is shown to be reduced to a new and nontrivial three-level Landau-Zener model.This nontrivial three-level Landau-Zener problem is then solved analytically by applying the integrability condition and symmetry considerations,and thus adds a new member to the few models that are exactly solvable.Based on the analytical results,the topological spin texture revealed by the time-averaged spin polarization can be applied to characterize the bulk topology and thus provides a direct comparison for future experiments.

On-the-Fly Nonadiabatic Dynamics of Caffeic Acid Sunscreen Compound

As a widely-used sunscreen com-pound,the caffeic acid(CA)shows the strong UV absorption,while the photoinduced reaction mecha-nisms behind its photoprotection ability are not fully understood.We try to investigate the photoin-duced internal conversion dynam-ics of CA in order to explore the photoprotection mechanism.The most stable CA isomer is selected to examine its nonadiabatic dy-namics using the on-the-fly surface hopping simulations at the semi-empirical level of electronic-struc-ture theory.The dynamics starting from different electronic states are simulated to explore the dependence of the photoinduced reaction channels on the excitation wavelengths.Several S1/S0 conical intersections,driven by the H-atom detachments and the ring deformations,have been found to be responsible for the nonadiabatic decay of the CA.The simulation re-sults show that the branching ratios towards these intersections are modified by the light with different excitation energies.This provides the valuable information for the understanding of the photoprotection mechanism of the CA compound.

Ion Nonthermality Induced Nonlinear Dust Acoustic Wave Propagation in a Complex Plasma in Presence of Weak Secondary Electron Emission from Dust Grains

In this paper we have investigated the effect of ion nonthermality on nonlinear dust acoustic wave propagation in a complex plasma in presence of weak secondary electron emission from dust grains. Equilibrium dust charge in this case is negative. Dusty plasma under our consideration consists of inertialess nonthermal ions, Boltzman distributed primary and secondary electrons and negatively charged inertial dust grains. Both adiabatic and nonadiabatic dust charge variations have been taken into account. Our analysis shows that in case of adiabatic dust charge variation, at a fixed non-zero ion nonthermality increasing secondary electron emission decreases amplitude and increases width of the rarefied dust acoustic soliton whereas for a fixed secondary electron yield increasing ion nonthermality increases amplitude and decreases width of such rarefied dust acoustic soliton. Thus shape of the soliton may be retained if strength of both the secondary electron yield and the ion nonthermality are increased. Nonadiabatic dust charge variation shows that, at fixed non-zero ion nonthermality, increasing secondary electron emission suppresses oscillation of oscillatory dust acoustic shock at weak nonadiabaticity and pronounces monotonicity of monotonic dust acoustic shock at strong nonadiabaticity. On the other hand at a fixed value of the secondary electron yield, increasing ion nonthermality enhances oscillation of oscillatory dust acoustic shock at weak nonadiabaticity and reduces monotonicity of monotonic dust acoustic shock at strong nonadiabaticity. Thus nature of dust acoustic shock may also remain unchanged if both secondary electron yield and ion nonthermality are increased.

Ultrafast Electron Transfer with Symmetrical Quasi-classical Dynamics based on Mapping Hamiltonian and Quantum Dynamics based on ML-MCTDH

Symmetrical quasi-classical （SQC） method based on mapping Hamiltonian is an efficient approach that is potentially useful to treat the nonadiabatic dynamics of very large systems. We try to evaluate the performance of this method in the ultrafast electron transfer processes involving a few of electronic states and a large number of vibrational modes. The multilayer multiconfigurational time-dependent Hartree （ML-MCTDH） method was used to get the accurate dynamical results for benchmark. Although the population dynamics in the long- time limit show differences in the ML-MCTDH and SQC calculations, the SQC method gives acceptable results.

Quantum Mechanics Rate Constant for the N-I-ND Reaction

We present nonadiabatic quantum dynamical calculations on the two coupled potential energy surfaces （12A＇ and 22A＇） [J. Theor. Comput. Chem. 8, 849 （2009）] for the reaction. Initial state-resolved reaction probabilities and cross sections for the N＋ND→N2＋D reaction and N＇＋ND→N＋N＇D reaction for collision energies of 5 meV to 1.0 eV are determined, respectively. It is found that the N＋ND→N2＋D reaction is dominated in the N＋ND reaction. In addition, we obtained the rate constants for the N＋ND→N2＋D reaction which demand further experimental investigations.

The instability of electrostatic wave in a magnetized dusty plasma with nonadiabatic dust charge fluctuation

The effects of external magnetized field and nonadiabatic dust charge fluctuation on instability of wave incorporating the nonthermally distributed ions and the temperatures of ion and dust in dusty plasmas are investigated. A linear dispersion relation is obtained. The numerical results show that the external magnetized field, fast ions and nonadiabatic dust charge fluctuation have strong influence on the frequency and the damping of wave.

A Theoretical Study on Nonadiabatic Trapping Models of the Reaction NH+H←→N+H_2

The properties of nonadiabatic trapping models of the reaction NH+H -N+H, are investigated in a collinear model as \veil as a non-collinear thermal reaction on the basis of theintrinsic reaction coordinate (IRC) intbrmation obtained by ah initio calculations at QCISD/631 IG** ie\el. Using the unitied statistical theory fornonadiabatic trapping models. the thermal rateconstants over the temperature range of 2000-3000K are computed which are in excellent agreementwith the experiment results.

Nonadiabatic Effect on the Rescattering Trajectories of Electrons in Strong Laser Field Ionization Process

The important features of the rescattering trajectories in strong field ionization process such as the cutoff of the return energy at 3.17Up and that of the final energy at 10Up are obtained, based on the adiabatic approximation in which the initial momentum of the electron is assumed to be zero. We theoretically study the nonadiabatic effect by assuming a nonzero initial momentum on the rescattering trajectories based on the semiclassical simpleman model. We show that the nonzero initial momentum will modify both the maximal return energy at collision and the final energy after backward scattering, but in different ways for odd and even number of return trajectories. The energies are increased for even number of returns but are decreased for odd number of returns when the nonzero （positive or negative） initial momentum is applied.

On Separation of Charges and Formation of Linear Structures in the Nuclei of Dislocations in Metals

In metals, the non-adiabatic mechanism of charge separation into the electron, cation, and vacancy chains is considered. It includes: 1) the photoelectric effect caused by bremsstrahlung caused by the scattering of conduction electrons by impurity ions lying at the ends of these chains and oscillating with the frequency of the local phonon mode;2) knocking out from the metal cations of the matrix, sufficiently slow (in comparison with the conduction electrons) photoelectrons that pull these cations from the nodes, thereby not violating the electroneutrality condition in the model of a free electron gas as with the static state of the chains and at their motion (slipping, recrawling) in the absence of a thermal field;3) induced radiation along the line of chains;4) the formation of linear structures in the spatial lattice of octahedral interstitial sites. The conditions for the formation of quasistable bound states in the dislocation core are considered. A hypothesis is advanced that the latent energy in the dislocation cores contains a component that is of an electromagnetic nature.

Nonadiabatic Population Transfer in a Tangent-Pulse Driven Quantum Model

Fine control of the dynamics of a quantum system is the key element to perform quantum information processing and coherent manipulations for atomic and molecular systems. We propose a control protocol using a tangentpulse driven model and demonstrate that it indicates a desirable design, i.e., of being both fast and accurate for population transfer. As opposed to other existing strategies, a remarkable character of the present scheme is that high velocity of the nonadiabatic evolution itself not only will not lead to unwanted transitions but also can suppress the error caused by the truncation of the driving pulse.

Three dimensional nonlinear shock waves in inhomogeneous plasmas with different size dust grains and external magnetized field

The evolution of three dimensional nonlinear shock waves is investigated in a dusty plasma with inhomogeneous particles’density,nonadiabatic dust charge variation,external magnetized field and power law dust size distribution.For this purpose,a modified nonlinear Korteweg-de Vries Burgers equation containing variable coefficients is obtained by reductive perturbation method.The effects of inhomogeneity,dust size distribution,external magnetized field,dust charge variation and obliqueness parameter on shock structures are numerically examined in great detail.Furthermore,research results show that oscillatory shock waves and monotone shock waves exist and transform each other in this system.

Photodissociation Exploration for Near-Visible UV Absorption of Molecular Bromine

The photodissociation of Br2 was investigated within the near-visible UV absorption band. Based on the potential curves for the ground and low-lying excited states, the optical cross-sections for the discrete transitions of C1^Пu,B^3Пou^＋, A^3П1u←X^1∑g＋ and their total energy absorption spectrum are derived, and the quantum yield of （Br＋Br6＊） channel are determined correspondingly. The one-dimensional Landau-Zener model is used to evaluate the behavior of curve crossing during photodissociation. The results indicate that the influence of nonadiabatic mechanism, which may be caused by the electronic-vibrational interplay between the 13 and C states, is negligibly small for the （Br＋Br^＊） channel. From the Landau-Zener modeling of the observed product recoil parameter β（Br＋Br）, the best-fit value of the coupling matrix elenment or coupling strength between the diabatic B and C state potentials is obtained.

Ab Initio Nonadiabatic Dynamics of Semiconductor Materials via Surface Hopping Method

Photoinduced carrier dynamic processes are without doubt the main driving force responsible for the efficient performance of semiconductor nanomaterials in applications like photoconversion and photonics.Nevertheless,establishing theoretical insights into these processes is computationally challenging owing to the multiple factors involved in the processes,namely reaction rate,material surface area,material composition etc.Modelling of photoinduced carrier dynamic processes can be performed via nonadiabatic molecular dynamics(NA-MD)methods,which are methods specifically designed to solve the time-dependent Schrodinger equation with the inclusion of nonadiabatic couplings.Among NA-MD methods,surface hopping methods have been proven to be a mighty tool to mimic the competitive nonadiabatic processes in semiconductor nanomaterials,a worth noticing feature is its exceptional balance between accuracy and computational cost.Consequently,surface hopping is the method of choice for modelling ultrafast dynamics and more complex phenomena like charge separation in Janus transition metal dichalcogenides-based van der Waals heterojunction materials.Covering latest stateof-the-art numerical simulations along with experimental results in the field,this review aims to provide a basic understanding of the tight relation between semiconductor nanomaterials and the proper simulation of their properties via surface hopping methods.Special stress is put on emerging state-ot-the-art techniques.By highlighting the challenge imposed by new materials,we depict emerging creative approaches,including high-level electronic structure methods and NA-MD methods to model nonadiabatic systems with high complexity.

Effect of conical intersection of benzene on non-adiabatic dynamics

The effect of conical intersection on the excited dynamics of benzene is studied by ab initio theory of electronic structure,which provides an important insight into photophysical and photochemical reactions.Based on the CASSCF(6,6)/6-31+G(d,p)method,the topological structures of conical intersections S_(1)/S and S_(2)/S_(1)of benzene,as well as the optimal structures of the ground state(S)and excited states(S_(1),S_(2)),are determined.The energy minima of the S_(1)state and S_(2)state are estimated at 4.608 e V and 6.889 e V,respectively.In addition,the energy values of the conical intersections of S_(1)/S and S_(2)/S_(1)are predicted to be 5.600 e V and 6.774 e V.According to the topological structures and energy values of the S_(2)/S_(1)and S_(1)/S conical intersections,the photophysical behavior of benzene excited to the S_(2)state and the effects of the S_(2)/S_(1)and S_(1)/S conical intersections are discussed in detail.

Understanding Photolysis of CH_(3)ONO_(2) with on-the-fly Nonadiabatic Dynamics Simulation at the ADC(2) Level

The nonadiabatic dynamics of methyl nitrate(CH_(3)ONO_(2))is studied with the on-the-fy trajectory surface hopping dynamics at the ADC(2)level.The results confirmed the existence of the ultrafast nonadiabatic decay to the electronic ground state.When the dynamics starts from S_(1) and S_(2),the photoproducts are CH_(3)O+NO_(2),consistent with previous results obtained from the experimental studies and theoretical dynamics simulations at more accurate XMS-CASPT2 level.The photolysis products are CH_(3)O+NO_(2) at the ADC(2)level when the dynamics starts from S3,while different photolysis products were obtained in previous experimental and theoretical works.These results demonstrate that the ADC(2)method may still be useful for treating the photolysis mechanism of CH_(3)ONO_(2) at the long-wavelength UV excitation,while great caution should be paid due to its inaccurate performance in the description of the photolysis dynamics at the short-wavelength UV excitation.This gives valuable information to access the accuracy when other alkyl nitrates are treated at the ADC(2)level.

The second dissociation threshold bound levels of hydrogen molecule

The near-threshold highly bound states of all three stable isotopic variants of molecular hydrogen have been studied. Numerous perturbations and unexpected transitions are observed as far as 1cm^-1 just below the second dissociation threshold. This complex structure may arise from a combination of nonadiabatic coupling between B, B＇, C electronic states, perturbations due to fine and hyperfine interactions, and strong shape resonances. The perturbed near-threshold states and vibrational continuum exhibit finegralned structure, differing greatly between isotopes because of varying nonadiabatic coupling.

Computational Characterization of Nanosystems

Nanosystems play an important role in many applications.Due to their complexity,it is challenging to accurately characterize their structure and properties.An important means to reach such a goal is computational simulation,which is grounded on ab initio electronic structure calculations.Low scaling and accurate electronic-structure algorithms have been developed in recent years.Especially,the efficiency of hybrid density functional calculations for periodic systems has been significantly improved.With electronic structure information,simulation methods can be developed to directly obtain experimentally comparable data.For example,scanning tunneling microscopy images can be effectively simulated with advanced algorithms.When the system we are interested in is strongly coupled to environment,such as the Kondo effect,solving the hierarchical equations of motion turns out to be an effective way of computational characterization.Furthermore,the first principles simulation on the excited state dynamics rapidly emerges in recent years,and nonadiabatic molecular dynamics method plays an important role.For nanosystem involved chemical processes,such as graphene growth,multiscale simulation methods should be developed to characterize their atomic details.In this review,we review some recent progresses in methodology development for computational characterization of nanosystems.Advanced algorithms and software are essential for us to better understand of the nanoworld.

Photodynamics of Methyl-Vinyl Criegee Intermediate:Different Conical Intersections Govern the Fates of Syn/Anti Configurations

Methyl vinyl ketone oxide,an unsaturated four-carbon Criegee intermediate produced from the ozonolysis of isoprene has been recognized to play a key role in determining the tropospheric OH concentration.It exists in four configurations(anti-anti,anti-syn,synanti,and syn-syn)due to two different substituents of saturated methyl and unsaturated vinyl groups.In this study,we have carried out the electronic structure calculation at the multi-configurational CASSCF and multi-state MS-CASPT2 levels,as well as the trajectory surface-hopping nonadiabatic dynamics simulation at the CASSCF level to reveal the different fates of syn/anti configurations in photochemical process.Our results show that the dominant channel for the S1-state decay is a ring closure,isomerization to dioxirane,during which,the syn(C-O)configuration with an intramolecular hydrogen bond shows slower nonadiabatic photoisomerization.More importantly,it has been found for the first time in photochemistry of Criegee intermediate that the cooperation of two heavy groups(methyl and vinyl)leads to an evident pyramidalization of C3 atom in methyl-vinyl Criegee intermediate,which then results in two structurally-independent minimal-energy crossing points(CIs)towards the syn(C-O)and anti(C-O)sides,respectively.The preference of surface hopping for a certain CI is responsible for the different dynamics of each configuration.

Linear and nonlinear excitations in complex plasmas with nonadiabatic dust charge fluctuation and dust size distribution

Both linear and nonlinear excitation in dusty plasmas have been investigated including the nonadiabatic dust charge fluctuation and Gaussian size distribution dust particles. A linear dispersion relation and a Korteweg-de Vries-Burgers equation governing the dust acoustic shock waves are obtained. The relevance of the instability of wave and the wave evolution to the dust size distribution and nonadiabatic dust charge fluctuation is illustrated both analytically and numerically. The numerical results show that the Gaussian size distribution of dust particles and the nonadiabatic dust charge fluctuation have strong common influence on the propagation of both linear and nonlinear excitations.