Electronic Relaxation Research Articles

Hot carrier relaxation dynamics of an aza-covalent organic framework during photoexcitation: An insight from abinitio quantum dynamics.

In order to develop an efficient metal-free solar energy harvester, we herein performed the electronic structure calculation, followed by the hot carrier relaxation dynamics of two dimensional (2D) aza-covalent organic framework by time domain density functional calculations in conjunction with non-adiabatic molecular dynamics (NAMD) simulation. The electronic structure calculation shows that the aza-covalent organic framework (COF) is a direct bandgap semiconductor with acute charge separation and effective optical absorption in the UV-visible region. Our study of non-adiabatic molecular dynamics simulation predicts the sufficiently prolonged electron-hole recombination process (6.8 nanoseconds) and the comparatively faster electron (22.48ps) and hole relaxation (0.51ps) dynamics in this two-dimensional aza-COF. According to our theoretical analysis, strong electron-phonon coupling is responsible for the rapid charge relaxation, whereas the electron-hole recombination process is slowed down by relatively weak electron-phonon coupling, relatively lower non-adiabatic coupling, and quick decoherence time. We do hope that our results of NAMD simulation on exciton relaxation dynamics will be helpful for designing photovoltaic devices based on this two dimensional aza-COF.

Magnetic Resonance Study of Bulky CVD Diamond Disc.

Diamonds produced using chemical vapor deposition (CVD) have found many applications in various fields of science and technology. Many applications involve polycrystalline CVD diamond films of micron thicknesses. However, a variety of optical, thermal, mechanical, and radiation sensing applications require more bulky CVD diamond samples. We report the results of a magnetic resonance and structural study of a thick, sizable polycrystalline CVD diamond disc, both as-prepared and treated with e-beam irradiation/high-temperature annealing, as well as gamma irradiation. The combination of various magnetic resonance techniques reveals and enables the attribution of a plentiful collection of paramagnetic defects of doublet and triplet spin origin. Analysis of spectra, electron, and nuclear spin relaxation, as well as nuclear spin diffusion, supports the conclusion of significant macro- and micro-inhomogeneities in the distribution of nitrogen-related defects.

Vibrational Motions in Ultrafast Electronic Relaxation of Pyrazine.

Ultrafast internal conversion via a conical intersection is ubiquitous in highly efficient photochemical reactions. Internal conversion from the 1ππ* to the 1nπ* state of pyrazine is the paradigm for this phenomenon; however, the relaxation occurs in such a short time (<20 fs) that the nuclear motion is difficult to observe in real time. The present study precisely measures the vibrational coherence transferred from the 1ππ* state to the 1nπ* state using time-resolved photoelectron spectroscopy with an unprecedented time resolution of 13.3 fs and reveals the key nuclear motions that drive the internal conversion.

Thickness-dependent electronic relaxation dynamics in solution-phase redox-exfoliated MoS2 heterostructures.

Electronic relaxation dynamics of solution-phase redox-exfoliated molybdenum disulfide (MoS2) monolayer and multilayer ensembles are described. MoS2 was exfoliated using polyoxometalate (POM) reductants. This process yields a colloidal heterostructure consisting of MoS2 2D sheet multilayers with surface-bound POM complexes. Using two-dimensional electronic spectroscopy, transient bleaching and photoinduced absorption signals were detected at excitation/detection energies of 1.82/1.87 and 1.82/1.80eV, respectively. Approximate 100-fs bandgap renormalization (BGR) and subsequent defect- and phonon-mediated relaxation on the picosecond timescale were resolved for several MoS2 thicknesses spanning from 1 to 2 L to ∼20 L. BGR rates were independent of sample thickness and slightly slower than observations for chemical vapor deposition-grown MoS2 monolayers. However, defect-mediated relaxation accelerated ∼10-fold with increased sample thicknesses. The relaxation rates increased from 0.33 ± 0.05 to 1.2 ± 0.1 and 3.1 ± 0.4ps-1 for 1-2 L, 3-4 L, and 20 L fractions. The thicknesses-dependent relaxation rates for POM-MoS2 heterostructures were modeled using a saturating exponential function that showed saturation at thirteen MoS2 layers. The results suggest that the increased POM surface coverage leads to larger defect density in the POM-MoS2 heterostructure. These are the first descriptions of the influence of sample thickness on electronic relaxation rates in solution-phase redox-exfoliated POM-MoS2 heterostructures. Outcomes of this work are expected to impact the development of solution-phase exfoliation of 2D metal-chalcogenide heterostructures.

Unified understanding of the breakdown of thermal mixing dynamic nuclear polarization: The role of temperature and radical concentration

We reveal an interplay between temperature and radical concentration necessary to establish thermal mixing (TM) as an efficient dynamic nuclear polarization (DNP) mechanism. We conducted DNP experiments by hyperpolarizing widely used DNP samples, i.e., sodium pyruvate-1-13C in water/glycerol mixtures at varying nitroxide radical (TEMPOL) concentrations and microwave irradiation frequencies, measuring proton and carbon-13 spin temperatures. Using a cryogen consumption-free prototype-DNP apparatus, we could probe cryogenic temperatures between 1.5 and 6.5 K, i.e., below and above the boiling point of liquid helium. We identify two mechanisms for the breakdown of TM: (i) Anderson type of quantum localization for low radical concentration, or (ii) quantum Zeno localization occurring at high temperature. This observation allowed us to reconcile the recent diverging observations regarding the relevance of TM as a DNP mechanism by proposing a unifying picture and, consequently, to find a trade-off between radical concentration and electron relaxation times, which offers a pathway to improve experimental DNP performance based on TM.

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.

Hypersonic boost-glide systems: Flight mechanics and plasma parameters evaluation through aero-thermo-chemical computational fluid dynamics

Currently, the conception, design, and development of hypersonic space-borne systems is a central topic of discussion among researchers and industrial stakeholders. In the design phase of a hypersonic manoeuvrable vehicle, it is essential to characterise the thermal heating and manage the problem of the communication blackout, in addition to other challenges concerning guidance, navigation and control, and propulsion. The interference of electromagnetic waves propagating in plasma affects the datalink and the radar detection of hypersonic targets. This work aims to provide valuable information about the aero-thermo-chemical behaviour of the fluid in the region around a hypersonic glider. Launch and re-entry phases of boost-glide systems have been modelled to perform trajectory predictions and assess range and flight paths under the effect of different manoeuvres, defining their possible performances. The resulting flight conditions are used to study the flow field surrounding a glider geometry similar to the Hypersonic Technology Vehicle-2. The thermodynamic and chemical fields around the body have been determined, and plasma parameters for novel electromagnetic interaction studies have been evaluated. Computational fluid dynamics simulations have been carried out to solve the averaged Navier-Stokes equations with the k−ω model for turbulent flows, coupled with the energy equation. Chemical non-equilibrium phenomena involving electronic energy relaxation as well as ionisation reactions have also been included. A gas mixture potentially composed of 11 species has been considered, namely oxygen and nitrogen derivatives. The electron number density is computed to evaluate the electron plasma and collision frequencies, essential parameters to characterise the electromagnetic interference caused by the plasma sheath. Among other results, high temperatures are reached at the nose region of the body in specific conditions of velocity and altitude, and non-negligible dissociation or ionisation of chemical species occurs. Plasma frequencies up to tens of GHz are reached in a region close to the body surface, while lower interference characterises the extended ionised wake.

Enhancement of thermoelectric performance in monolayer AlP3 via Ga and In doping: A first-principles study

Recently, two-dimensional (2D) triphosphides have attracted much attention in the thermoelectric field due to their semiconductor properties and excellent electronic transport properties. In our study, the performances of AlP3, Al0.5Ga0.5P3, and Al0.5In0.5P3 doped monolayers in the thermoelectric transport are studied. First, the dynamic structural stabilities of the three monolayers are verified through phonon dispersion curves. Moreover, all monolayers are indirect band-gap semiconductors, which can be used as thermoelectric materials. The results show that larger electronic relaxation time and carrier mobilities of doped monolayers lead to larger electronic transport parameters and higher dimensionless thermoelectric figure-of-merit (ZT). It is found that after doping via Ga and In, the thermoelectric performances of AlP3 are increased by 1.31–1.79 times. Our findings show that AlP3 and its doped monolayers hold significant promise as thermoelectric materials within the temperature span of 300–700 K and the doping mechanism could significantly improve the thermoelectric properties of 2D structures.

Unraveling Electron Dynamics in p-type Indium Phosphide (100): A Time-Resolved Two-Photon Photoemission Study.

Renewable ("green") hydrogen production through direct photoelectrochemical (PEC) water splitting is a potential key contributor to the sustainable energy mix of the future. We investigate the potential of indium phosphide (InP) as a reference material among III-V semiconductors for PEC and photovoltaic (PV) applications. The p(2 × 2)/c(4 × 2)-reconstructed phosphorus-terminated p-doped InP(100) (P-rich p-InP) surface is the focus of our investigation. We employ time-resolved two-photon photoemission (tr-2PPE) spectroscopy to study electronic states near the band gap with an emphasis on normally unoccupied conduction band states that are inaccessible through conventional single-photon emission methods. The study shows the complexity of the p-InP electronic band structure and reveals the presence of at least nine distinct states between the valence band edge and vacuum energy, including a valence band state, a surface defect state pinning the Fermi level, six unoccupied surface resonances within the conduction band, as well as a cluster of states about 1.6 eV above the CBM, identified as a bulk-to-surface transition. Furthermore, we determined the decay constants of five of the conduction band states, enabling us to track electron relaxation through the bulk and surface conduction bands. This comprehensive understanding of the electron dynamics in p-InP(100) lays the foundation for further exploration and surface engineering to enhance the properties and applications of p-InP-based III-V-compounds for, e.g., efficient and cost-effective PEC hydrogen production and highly efficient PV cells.

Electron-phonon coupling dictates electron mean free paths and negative thermal diffusion in metals

The spatiotemporal dynamics of the fundamental energy carriers in metals underpin the efficiency of a wide array of technologies. Although much progress in our understanding of the temporal response of electronic relaxation processes following an external field perturbation has been achieved, the spatial relaxation dynamics of electrons after excitation remains unclear. Here, we employ a scanning ultrafast microscopy with high spatial resolution to directly measure the mean free paths of electrons in different metals. We show that the strength of electron-phonon coupling not only dictates the mean free paths, but also controls a peculiar spatial shrinking of the electronic temperature profile immediately after the electrons have thermalized with the ‘colder’ lattice. More specifically, from our experimental tracking of the spatial relaxation profiles, a clear observation of an effective negative thermal diffusion is apparent for metals with weaker electron-phonon coupling, while for metals with stronger electron-phonon coupling, the negative thermal diffusion effect is not observable. Our spatiotemporal modeling based on the two-temperature approach provides evidence that although negative diffusion occurs universally for materials with two different species that have varying diffusivities and are thermodynamically coupled, effective negative diffusion is masked for cases with stronger coupling between the species.

Excitation energy transfer and vibronic relaxation through light-harvesting dendrimer building blocks: A nonadiabatic perspective.

The light-harvesting excitonic properties of poly(phenylene ethynylene) (PPE) extended dendrimers (tree-like π-conjugated macromolecules) involve a directional cascade of local excitation energy transfer (EET) processes occurring from the "leaves" (shortest branches) to the "trunk" (longest branch), which can be viewed from a vibronic perspective as a sequence of internal conversions occurring among a connected graph of nonadiabatically coupled locally excited electronic states via conical intersections. The smallest PPE building block that is able to exhibit EET, the asymmetrically meta-substituted PPE oligomer with one acetylenic bond on one side and two parallel ones on the other side (hence, 2-ring and 3-ring para-substituted pseudo-fragments), is a prototype and the focus of the present work. From linear-response time-dependent density functional theory electronic-structure calculations of the molecule as regards its first two nonadiabatically coupled, optically active, singlet excited states, we built a (1 + 2)-state-8-dimensional vibronic-coupling Hamiltonian model for running subsequent multiconfiguration time-dependent Hartree wavepacket relaxations and propagations, yielding both steady-state absorption and emission spectra as well as real-time dynamics. The EET process from the shortest branch to the longest one occurs quite efficiently (about 80% quantum yield) within the first 25fs after light excitation and is mediated vibrationally through acetylenic and quinoidal bond-stretching modes together with a particular role given to the central-ring anti-quinoidal rock-bending mode. Electronic and vibrational energy relaxations, together with redistributions of quantum populations and coherences, are interpreted herein through the lens of a nonadiabatic perspective, showing some interesting segregation among the foremost photoactive degrees of freedom as regards spectroscopy and reactivity.

1H Spin-Lattice Relaxation Processes in Solutions of H2N-Fe3O4 Nanoparticles: Insights from NMR Relaxometry.

1H spin-lattice relaxation experiments have been performed for water and glycerol/water solutions of H2N-Fe3O4 superparamagnetic nanoparticles (NPs) of about 7 nm diameter. The experiments encompass a broad frequency range covering 3 orders of magnitude, from 10 kHz to 10 MHz (referring to 1H resonance frequency), and have been performed in the temperature range from 298 to 313 K, varying the concentration of the superparamagnetic species. This extensive dataset has been used for twofold purposes. The first one is to serve as a challenge for thorough tests of theoretical models describing nuclear relaxation in solutions of superparamagnetic NPs, depending on their magnetic properties and dynamics of the solvent molecules. The challenge is posed by the wish to reproduce the data in a broad range of magnetic fields (not only at high fields) and by the need to explain the differences in the relaxation scenarios for water and glycerol/water solutions by varying only the solvent parameters. The second purpose is to get insights into the magnetic properties (electronic relaxation properties) of the nanoparticles due to their high applicational potential.

Quantum tomography of molecules using ultrafast electron diffraction.

We propose a quantum tomography (QT) approach to retrieve the temporally evolving reduced density matrix in electronic state basis, where the populations and coherence between the ground state and excited state are reconstructed from the ultrafast electron diffraction signal. In order to showcase the capability of the proposed QT approach, we simulate the nuclear wavepacket dynamics and ultrafast electron diffraction of photoexcited pyrrole molecules using the abinitio quantum chemical CASSCF method. From the simulated time-resolved diffraction data, we retrieve the evolving density matrix in a crude diabatic representation basis and reveal the symmetry of the excited pyrrole wavepacket. Our QT approach opens the route to make a quantum version of "molecular movie" that covers the electronic degree of freedom and equips ultrafast electron diffraction with the power to reveal the coherence between electronic states, relaxation, and dynamics of population transfer.

Coherent Carrier Spin Dynamics in FAPbBr3 Perovskite Crystals.

Coherent spin dynamics of electrons and holes are studied in hybrid organic-inorganic lead halide perovskite FAPbBr3 bulk single crystals using the time-resolved Kerr ellipticity technique at cryogenic temperatures. The Larmor spin precession of the carrier spins in a magnetic field is monitored to measure the Landé g-factors of electrons (+2.44) and holes (+0.41). These g-factors are highly isotropic. The measured spin dephasing times amount to a few nanoseconds, and the longitudinal hole spin relaxation time is 470 ns. The important role of the strong hyperfine interaction between carrier spins and nuclear spins is demonstrated via dynamic nuclear polarization. At low temperatures, electron and hole spin relaxation predominantly occurs via the hyperfine interaction, whose importance significantly decreases at temperatures above 12 K. We overview the spin dynamics in various lead halide perovskite crystals and polycrystalline films and conclude on their common features provided by charge carrier localization at cryogenic temperatures.

Ultrafast and Multichannel Generation of the Triplet State in DNA-Intercalated Gilvocarcin V for an Enhanced Photoaddition Reaction.

Gilvocarcin V (GV) is a natural antibiotic exhibiting excellent antitumor activities and remarkably low toxicity in near-ultraviolet or visible light-dependent treatment. Notwithstanding, the [2 + 2] cycloaddition reaction between GV and thymine has been proven to be the key for its function in photodynamic therapy, and crucial mechanistic details about such a reaction are poorly understood. In this study, the electronic relaxation pathways and photoaddition reaction are characterized by femto- to nanosecond time-resolved spectroscopy combined with quantum chemical calculation. Our results reveal that ultrafast intersystem crossing (<3 ps) leads to the population of a local triplet excited state in DNA-intercalated GV. Such a state can further induce the formation of a biradical state, which is identified as the important reactive precursor for photoaddition between GV and thymine. The overall photoaddition quantum efficiency is determined to be 11.57 ± 1.0%. These results are essential to the elucidation of the DNA photoaddition mechanism of C-aryl glycoside-based artificial photocytotoxic agents and could help further development of those medicines.

Diamond for High-Power, High-Frequency, and Terahertz Plasma Wave Electronics.

High thermal conductivity and a high breakdown field make diamond a promising candidate for high-power and high-temperature semiconductor devices. Diamond also has a higher radiation hardness than silicon. Recent studies show that diamond has exceptionally large electron and hole momentum relaxation times, facilitating compact THz and sub-THz plasmonic sources and detectors working at room temperature and elevated temperatures. The plasmonic resonance quality factor in diamond TeraFETs could be larger than unity for the 240-600 GHz atmospheric window, which could make them viable for 6G communications applications. This paper reviews the potential and challenges of diamond technology, showing that diamond might augment silicon for high-power and high-frequency compact devices with special advantages for extreme environments and high-frequency applications.

Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane

The light-induced ultrafast switching between molecular isomers norbornadiene and quadricyclane can reversibly store and release a substantial amount of chemical energy. Prior work observed signatures of ultrafast molecular dynamics in both isomers upon ultraviolet excitation but could not follow the electronic relaxation all the way back to the ground state experimentally. Here we study the electronic relaxation of quadricyclane after exciting in the ultraviolet (201 nanometres) using time-resolved gas-phase extreme ultraviolet photoelectron spectroscopy combined with non-adiabatic molecular dynamics simulations. We identify two competing pathways by which electronically excited quadricyclane molecules relax to the electronic ground state. The fast pathway (<100 femtoseconds) is distinguished by effective coupling to valence electronic states, while the slow pathway involves initial motions across Rydberg states and takes several hundred femtoseconds. Both pathways facilitate interconversion between the two isomers, albeit on different timescales, and we predict that the branching ratio of norbornadiene/quadricyclane products immediately after returning to the electronic ground state is approximately 3:2.

Two-Step Relaxation of Non-Equilibrium Electrons in Graphene: The Key to Understanding Pump–Probe Experiments

In the majority of experiments targeting nonlinear optical phenomena, the application of high-intensity pulses drives electrons in graphene into a strongly non-equilibrium state. Under these conditions, conventional perturbation theory falls short in explaining graphene’s intricate optical response because of significant deviations in electron distribution over energy states from the equilibrium Fermi-Dirac one. In this work, we present a two-step relaxation model capable of predicting the transient dynamics of graphene’s carriers out of equilibrium, from the generation of spectrally narrow populations of non-thermalized electrons and holes to the establishment of a hot-electron gas and its subsequent cooling toward equilibrium with the crystal lattice. By comparing our model calculations to experimental results, we demonstrate its reliability and relevance to pump–probe experiments, providing insights into the pivotal role of hot electrons in comprehending ultrafast dynamics in graphene.

Ultrafast hot-carrier dynamics in ultrathin monocrystalline gold

Applications in photodetection, photochemistry, and active metamaterials and metasurfaces require fundamental understanding of ultrafast nonthermal and thermal electron processes in metallic nanosystems. Significant progress has been recently achieved in synthesis and investigation of low-loss monocrystalline gold, opening up opportunities for its use in ultrathin nanophotonic architectures. Here, we reveal fundamental differences in hot-electron thermalisation dynamics between monocrystalline and polycrystalline ultrathin (down to 10 nm thickness) gold films. Comparison of weak and strong excitation regimes showcases a counterintuitive unique interplay between thermalised and non-thermalised electron dynamics in mesoscopic gold with the important influence of the X-point interband transitions on the intraband electron relaxation. We also experimentally demonstrate the effect of hot-electron transfer into a substrate and the substrate thermal properties on electron-electron and electron-phonon scattering in ultrathin films. The hot-electron injection efficiency from monocrystalline gold into TiO2, approaching 9% is measured, close to the theoretical limit. These experimental and modelling results reveal the important role of crystallinity and interfaces on the microscopic electronic processes important in numerous applications.

Luminescent Radicals.

Organic radicals are attracting increasing interest as a new class of molecular emitters. They demonstrate electronic excitation and relaxation dynamics based on their doublet or higher multiplet spin states, which are different from those based on singlet-triplet manifolds of conventional closed-shell molecules. Recent studies have disclosed luminescence properties and excited state dynamics unique to radicals, such as highly efficient electron-photon conversion in OLEDs, NIR emission, magnetoluminescence, an absence of heavy atom effect, and spin-dependent and spin-selective dynamics. These are difficult or sometimes impossible to achieve with closed-shell luminophores. This review focuses on luminescent organic radicals as an emerging photofunctional molecular system, and introduces the material developments, fundamental properties including luminescence, and photofunctions. Materials covered in this review range from monoradicals, radical oligomers, and radical polymers to metal complexes with radical ligands demonstrating radical-involved emission. In addition to stable radicals, transiently formed radicals generated in situ by external stimuli are introduced. This review shows that luminescent organic radicals have great potential to expand the chemical and spin spaces of luminescent molecular materials and thus broaden their applicability to photofunctional systems.