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Abstract Effective photoinduced charge transfer makes molecular bimetallic assemblies attractive for applications as active light‐induced proton reduction systems. Developing competitive base metal dyads is mandatory for a more sustainable future. However, the electron transfer mechanisms from the photosensitizer to the proton reduction catalyst in base metal dyads remain so far unexplored. A Fe─Co dyad that exhibits photocatalytic H2 production activity is studied using femtosecond X‐ray emission spectroscopy, complemented by ultrafast optical spectroscopy and theoretical time‐dependent DFT calculations, to understand the electronic and structural dynamics after photoexcitation and during the subsequent charge transfer process from the FeII photosensitizer to the cobaloxime catalyst. This novel approach enables the simultaneous measurement of the transient X‐ray emission at the iron and cobalt K‐edges in a two‐color experiment. With this methodology, the excited state dynamics are correlated to the electron transfer processes, and evidence of the Fe→Co electron transfer as an initial step of proton reduction activity is unraveled.

Abstract Chorus waves are intense electromagnetic emissions critical in modulating electron dynamics. In this study, we perform two‐dimensional particle‐in‐cell simulations to investigate self‐consistent wave‐particle interactions with oblique chorus waves. We first analyze the electron dynamics sampled from cyclotron and Landau resonances with waves, and then quantify the advection and diffusion coefficients through statistical studies. It is found that phase‐trapped cyclotron resonant electrons satisfy the second‐order resonance condition and gain energy from waves. While phase‐bunched cyclotron resonant electrons cannot remain in resonance for long periods. They transfer energy to waves and are scattered to smaller pitch angles. Landau resonant electrons are primarily energized by waves. For both types of resonances, advection coefficients are greater than diffusion coefficients when the wave amplitude is large. Our study highlights the important role of advection in electron dynamics modulation resulting from nonlinear wave‐particle interactions.

Abstract Chorus subpackets are the wave packets with modulated amplitudes in chorus waves, commonly observed in the magnetospheres of Earth and other planets. Nonlinear wave‐particle interactions have been suggested to play an important role in subpacket formation, yet the corresponding electron dynamics remain not fully understood. In this study, we have investigated the electron trapping through cyclotron resonance with subpackets, using a self‐consistent general curvilinear plasma simulation code simulation model in dipole fields. The electron trapping period has been quantified separately through electron dynamic analysis and theoretical derivation. Both methods indicate that the electron trapping period is shorter than the subpacket period/duration. We have further established the relation between electron trapping period and subpacket period through statistical analysis using simulation and observational data. Our study demonstrates that the nonlinear electron trapping through cyclotron resonance is the dominant mechanism responsible for subpacket formation.

Abstract With high‐resolution data from Magnetospheric Multiscale (MMS) mission, an ion‐scale flux rope (FR) with a heavily tilted axis is observed in the tailward outflow of a magnetic reconnection in the terrestrial magnetotail. Combined with the field‐aligned electron distribution and positions of MMS when the X‐line and FR are observed, the tilted axis is inferred to be caused by the extension of the X‐line in the dawn‐dusk direction. J · E′ is negative and electrons are losing energy in the FR. An ion‐scale electron vortex embedded in the plane perpendicular to the axis is observed inside FR. The induced magnetic field generated by the electron vortex has the same direction as the axial component, which can contribute to the axial component and increase the magnetic flux of the FR. Such electron vortex FRs may be an essential carrier of magnetic flux from near‐Earth X‐line to distant X‐line or interplanetary space.

Abstract Dipolarization fronts (DFs) have been suggested as crucial energy conversion sites contributing significantly to global energy transfer in the magnetosphere. However, energy partitioning of DF‐driven energy transfer remains hitherto elusive. Using high‐cadence data from MMS spacecraft, we present a detailed investigation of energy flux densities at two DFs with/without surface ripples. We find that during both DF intervals, electron enthalpy flux increases dramatically, carries the greatest energy, and well correlates with local energy conversion. Poynting flux also increases but contributes to a relatively smaller portion. Ion enthalpy flux which in magnitude is slightly smaller than electron enthalpy flux barely changes. Particle kinetic energy and heat fluxes are negligible. Strong difference in energy fluxes observed by different spacecraft is found at the rippled DF, indicating three‐dimensional energy transport. These results indicate that energy budgets at the DFs are dominated by electron physics, rather than ion dynamics suggested by previous studies.

A pair of simulated left and right circularly polarized ultra-fast laser pulses of duration 20 femtoseconds that induce a mixture of excited states are applied to ethane. The response of the electron dynamics is investigated within the next generation quantum theory of atoms in molecules (NG-QTAIM) using third-generation eigenvector-trajectories which are introduced in this work. This enables an analysis of the mechanical and chiral properties of the electron dynamics of ethane without needing to subject the C-C bond to external torsions as was the case for second-generation eigenvector-trajectories. The mechanical properties, in particular, the bond-flexing and bond-torsion were found to increase depending on the plane of the applied laser pulses. The bond-flexing and bond-torsion, depending on the plane of polarization, increases or decreases after the laser pulses are switched off. This is explainable in terms of directionally-dependent effects of the long-lasting superpositions of excited states. The chiral properties correspond to the ethane molecule being classified as formally achiral consistent with previous NG-QTAIM investigations. Future planned investigations using ultra-fast circularly polarized lasers are briefly discussed., (© 2023 Wiley Periodicals LLC.)

We present a new implementation of real-time time-dependent density functional theory (RT-TDDFT) for calculating excited-state dynamics of periodic systems in the open-source Python-based PySCF software package. Our implementation uses Gaussian basis functions in a velocity gauge formalism and can be applied to periodic surfaces, condensed-phase, and molecular systems. As representative benchmark applications, we present optical absorption calculations of various molecular and bulk systems and a real-time simulation of field-induced dynamics of a (ZnO) 4 molecular cluster on a periodic graphene sheet. We present representative calculations on optical response of solids to infinitesimal external fields as well as real-time charge-transfer dynamics induced by strong pulsed laser fields. Due to the widespread use of the Python language, our RT-TDDFT implementation can be easily modified and provides a new capability in the PySCF code for real-time excited-state calculations of chemical and material systems., (© 2022 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.)

An implementation of real-time time-dependent density functional theory (RT-TDDFT) within the TURBOMOLE program package is reported using Gaussian-type orbitals as basis functions, second and fourth order Magnus propagator, and the self-consistent field as well as the predictor-corrector time integration schemes. The Coulomb contribution to the Kohn-Sham matrix is calculated combining density fitting approximation and the continuous fast multipole method. Performance of the implementation is benchmarked for molecular systems with different sizes and dimensionalities. For linear alkane chains, the wall time for density matrix time propagation step is comparable to the Kohn-Sham (KS) matrix construction. However, for larger two- and three-dimensional molecules, with up to about 5,000 basis functions, the computational effort of RT-TDDFT calculations is dominated by the KS matrix evaluation. In addition, the maximum time step is evaluated using a set of small molecules of different polarities. The photoabsorption spectra of several molecular systems calculated using RT-TDDFT are compared to those obtained using linear response time-dependent density functional theory and coupled cluster methods., (© 2020 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.)

Using state-of-the-art antisymmetrized multiconfiguration time-dependent Hartree (MCTDH) electron dynamics calculations we study the interdependence of the intermolecular Coulombic decay (ICD) process on the geometric parameters of a doubly-charged paired quantum dot (PQD) model system in the framework of the effective mass approximation (EMA). We find that ICD displays a maximum rate for a certain geometry of the electron-emitting quantum dot, which is simultaneously dependent on both the distance between the quantum dots as well as the photon-absorbing quantum dot's geometry. The rate maximum is shown to be caused by the competing effects of polarization of electron density and Coulomb repulsion. The ICD rate-maximized PQD geometry in GaAs QDs yields a decay time of 102.39 ps. It is given by two vertically-aligned cylindrical QDs with radii of 14.42 nm separated by 86.62 nm. The photon absorbing QD then has a height of 46.59 nm and the electron emitting QD a height of 16.33 nm. © 2017 Wiley Periodicals, Inc., (© 2017 Wiley Periodicals, Inc.)