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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Tracking dissociation pathways of nitrobenzene via mega-electron-volt ultrafast electron diffraction

As the simplest nitroaromatic compound, nitrobenzene is an interesting model system to explore the rich photochemistry of nitroaromatic compounds. Previous investigations of nitrobenzene's photochemical dynamics have probed structural and electronic properties. These investigations paint, at times, a convoluted and sometimes contradictory description of the photochemical landscape. Here, we investigate the ultrafast dynamics of nitrobenzene triggered by photoexcitation at 267 nm for the first time using a structural probe with femtosecond time resolution. Our probe complements previous measurements of nitrobenzene's electronic structure evolution and aids in determining the photochemical dynamics with less ambiguity. We employ megaelectronvolt ultrafast electron diffraction to follow nitrobenzene's structural evolution within the first 5 ps after photoexcitation. We observe ground state recovery within 160 ± 60 fs through nonadiabatic dynamics. Based on comparisons of the experimental signal with molecular dynamics simulations, we exclude a significant population of the triplet manifold. Furthermore, we do not observe fragmentation of nitrobenzene within the investigated time window, which indicates that previously observed photofragmentation reactions take place in the vibrationally 'hot' ground state on timescales considerably beyond 5 ps.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

X-ray free electron laser studies of electron and phonon dynamics of graphene adsorbed on copper

Here, we report optical pumping and x-ray absorption spectroscopy experiments at the Pohang Accelerator Laboratory free electron laser that probes the electron dynamics of a graphene monolayer adsorbed on copper in the femtosecond regime. By analyzing the results with ab initio theory we infer that the excitation of graphene is dominated by indirect excitation from hot electron-hole pairs created in the copper by the optical laser pulse. However, once the excitation is created in graphene, its decay follows a similar path as in many previous studies of graphene adsorbed on semiconductors, i.e., rapid excitation of strongly coupled optical phonons and eventual thermalization. It is likely that the lifetime of the hot electron-hole pairs in copper governs the lifetime of the electronic excitation of the graphene.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Lessons from combined experimental and theoretical examination of the FTIR and 2D-IR spectroelectrochemistry of the amide I region of cytochrome c</em

Amide I difference spectroscopy is widely used to investigate protein function and structure changes. In this article, we show that the common approach of assigning features in amide I difference signals to distinct secondary structure elements in many cases may not be justified. Evidence comes from Fourier transform infrared (FTIR) and 2D-IR spectroelectrochemistry of the protein cytochrome c in the amide I range, in combination with computational spectroscopy based on molecular dynamics (MD) simulations. This combination reveals that each secondary structure unit, such as an alpha-helix or a beta-sheet, exhibits broad overlapping contributions, usually spanning a large part of the amide I region, which in the case of difference absorption experiments (such as in FTIR spectroelectrochemistry) may lead to intensity-compensating and even sign-changing contributions. We use cytochrome c as the test case, as this small electron-transferring redox-active protein contains different kinds of secondary structure units. Upon switching its redox-state, the protein exhibits a different charge distribution while largely retaining its structural scaffold. Our theoretical analysis suggests that the change in charge distribution contributes to the spectral changes and that structural changes are small. However, in order to confidently interpret FTIR amide I difference signals in cytochrome c and proteins in general, MD simulations in combination with additional experimental approaches such as isotope labeling, the insertion of infrared labels to selectively probe local structural elements will be required. In case these data are not available, a critical assessment of previous interpretations of protein amide I 1D- and 2D-IR difference spectroscopy data is warranted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Plasmon-Induced Hot-Carrier Excited-State Dynamics in Plasmonic Semiconductor Nanocrystals

The variance of carrier relaxation pathways for WO 3–x plasmonic semiconductor nanocrystals (PSNCs) is monitored by transient absorption spectroscopy following excitation of the localized surface plasmon resonance (LSPR) versus the optical band gap (E g,opt ). Excitation of the LSPR leads to efficient hot carrier population above the Fermi level in WO 3–x via Landau damping, in analogy to noble metal LSPR relaxation mechanisms. Hot carrier depopulation occurs on the femtosecond timescale, observed as the concomitant recovery of an LSPR bleach with the appearance of discrete interband and intraband photoinduced absorption features. Further, by comparison, the direct excitation of E g,opt results in trion recombination at donor–acceptor sites within the WO 3–x NC, consistent with exciton decay dynamics observed for typical wide-band-gap semiconductor NCs. From the analysis of pump power dependency data, a hot-carrier electron–phonon coupling constant of 1.47 × 10 11 J K –1 s –1 cm –3 is extracted. The direct comparison of the decay dynamics following E g,opt versus LSPR excitation confirms that the observed plasmon in trioctylphosphine oxide passivated, spherical WO 3–x is a resonance state in which hot carriers are generated only from excitation on resonance with the LSPR frequency. This study on WO 3–x PSNCs provides a toolset that can be used to evaluate the role of hot carriers following LSPR excitation of n-type, plasmonic transparent conducting oxide NCs, where enhancement of photocatalysis, photovoltaic performance, and optical enhancement has been reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Ultrafast formation of topological defects in a two-dimensional charge density wave

Topological defects play a central role in dynamical systems undergoing a non-adiabatic transition. In solids, topological defects as a result of femtosecond laser excitation have attracted increasing interest not only because they are key to understanding phase transitions but also because they can generate a variety of hidden orders that are not accessible in thermal equilibrium. Despite the common occurrence of these defects in a non-equilibrium system, the fundamental limit on how fast they can emerge in solids and the generic pathway for defect creation at such fast timescales have remained open questions. Here we apply ultrafast electron diffraction to study the reciprocal-space signatures of transient defects in a two-dimensional charge density wave, where simultaneous measurements of both defect and phonon dynamics yield a microscopic view of defect formation in the femtosecond regime. We find that one-dimensional domain walls are generated well within 1 ps following photoexcitation, during which the defect growth is not dictated by the amplitude of the order parameter but is mediated by a non-thermal population of longitudinal optical phonons. In conclusion, our work provides a framework for the ultrafast engineering of topological defects that are coupled to specific collective modes, which will prove useful for the dynamical control of non-equilibrium phases in correlated materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Ultrafast signatures of spin and orbital order in antiferromagnetic α-Sr2CrO4

Abstract The antiferromagnetic Mott insulator α -Sr 2 CrO 4 possesses multiple spin and orbital ordered phases, but their unique interplay is still relatively unexplored. Here, we used femtosecond optical spectroscopy to study ultrafast spin and orbital ordering dynamics in α -Sr 2 CrO 4 through their non-equilibrium response to photoexcitation. By varying the pump photon energy, we selectively drove inter-site spin hopping between neighboring Cr t 2 g orbitals and charge transfer-type transitions between oxygen 2 p and Cr e g orbitals. The resulting transient reflectivity dynamics revealed temperature-dependent anomalies across the Néel temperature for spin ordering as well as the transition temperatures linked to different types of orbital order. Our results reveal distinct relaxation timescales for spin and orbital orders in α -Sr 2 CrO 4 and provide experimental evidence for the phase transition at T O , possibly related to antiferro-type orbital ordering.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Symmetry-dependent ultrafast manipulation of nanoscale magnetic domains

Symmetry is a powerful concept in physics, but its applicability to far-from-equilibrium states is still being understood. Recent attention has focused on how far-from-equilibrium states lead to spontaneous symmetry breaking. Conversely, ultrafast optical pumping can be used to drastically change the energy landscape and quench the magnetic order parameter in magnetic systems. Here, we find a distinct symmetry-dependent ultrafast behaviour by use of ultrafast x-ray scattering from magnetic patterns with varying degrees of isotropic and anisotropic symmetry. After pumping with an optical laser, the scattered intensity reveals a radial shift exclusive to the isotropic component and exhibits a faster recovery time from quenching for the anisotropic component. These features arise even when both symmetry components are concurrently measured, suggesting a correspondence between the excitation and the magnetic order symmetry. Our results underline the importance of symmetry as a critical variable to manipulate the magnetic order in the ultrafast regime.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1996

Computational Modeling of Ultrafast Pulse Propagation in Nonlinear Optical Materials

There is an emerging technology of photonic (or optoelectronic) integrated circuits (PICs or OEICs). In PICs, optical and electronic components are grown together on the same chip. rib build such devices and subsystems, one needs to model the entire chip. Accurate computer modeling of electromagnetic wave propagation in semiconductors is necessary for the successful development of PICs. More specifically, these computer codes would enable the modeling of such devices, including their subsystems, such as semiconductor lasers and semiconductor amplifiers in which there is femtosecond pulse propagation. Here, the computer simulations are made by solving the full vector, nonlinear, Maxwell's equations, coupled with the semiconductor Bloch equations, without any approximations. The carrier is retained in the description of the optical pulse, (i.e. the envelope approximation is not made in the Maxwell's equations), and the rotating wave approximation is not made in the Bloch equations. These coupled equations are solved to simulate the propagation of femtosecond optical pulses in semiconductor materials. The simulations describe the dynamics of the optical pulses, as well as the interband and intraband.

Goorjian, Peter M.↗
DOE OSTI2025

Tuning Solvation Dynamics of Electrolytes at Their Eutectic Point Through Halide Identity

Deep eutectic solvents (DESs) are regarded as highly promising solvent systems for redox flow batteries. DESs, composed of choline halides (ChX, X = F − , Cl − , Br − , I − ) and ethylene glycol (EG), exhibit distinct physicochemical properties at their eutectic points, including halide-dependent phase behavior, viscosity, polarity, conductivity, and solvation dynamics. In this study, we investigate the effects of the halide identity on the solvation properties of ChX:EG mixtures at varying mol % of ChX salt content. The solvatochromic polarity based on ET(30) measurements indicates higher polarity for larger halides (I − > Br − ) than for smaller halides (Cl − > F − ), which exhibit larger compensating solvation shells. The ionic conductivity follows the trend of the solvent fluidity (the inverse of the viscosity), namely ChCl > ChBr > ChI > ChF, influenced by the ion mobility and solvodynamic radii. Measurements of the liquidus temperatures (T L ) reveal that the system with ChCl exhibits the deepest eutectic point (at ~20 mol % ChCl), while ChBr and ChI have shallower minima at ~10 mol % ChBr and ~3 mol % ChI, respectively. ChF does not display a eutectic transition but instead appears to readily supercool at salt concentrations above 30 mol % ChF. Consistent with the phase transition measurements, femtosecond transient absorption spectroscopy shows that in the ChCl system, the solvation dynamics become faster with an increasing salt concentration up to ~16.67 mol %, after which the dynamics slow down with further increases in the salt content. The ChF-based system exhibits similar behavior, though with slower dynamics. In contrast, the solvation dynamics of the systems containing ChBr and ChI monotonously slow down with an increasing salt concentration, in agreement with the phase transition measurements, which show that the eutectic points occur at low salt concentrations. These measurements suggest that the solvent composition and, in particular, the identity of the halide anion play a significant role in the solvation behavior of these ethylene-glycol-based DESs, offering a foundation for tuning the DES properties for specific applications.

Biochemistry & Molecular Biology↗
DOE OSTI2025

Ultrafast-induced coherent acoustic phonons in the two-dimensional magnet CrSBr

Magnetism in two-dimensional (2D) van der Waals (vdW) crystals offers promising new directions for low-dimensional physics and devices. In this work, mega-electron volt (MeV) ultrafast electron diffraction was employed to investigate the ultrafast atomic dynamics of a novel, 2D vdW magnetic single-crystal CrSBr. Femtosecond (fs) optical pump pulses excited non-equilibrium atomic displacements shown to be coherent acoustic phonons (CAPs). Phonon frequencies were extracted by analyzing oscillations of different Bragg peak (BP) intensities and were determined to be GHz acoustic disturbances that propagated as strain waves. Phonon modes exhibit anisotropy with respect to the a and b crystal axes. Subharmonic phonon frequencies were also observed, and this provided a signature of nonlinear oscillatory coupling between the laser-induced pumping phonon frequency and secondary phonon frequencies. Thus, CrSBr was found to serve as a nonlinear phononic frequency converter. The ultrafast time dependence of the Bragg intensity was simulated by incorporating an oscillating deviation parameter ansatz into expressions for the dynamical scattering intensity yielded excellent modeling of the ultrafast structural dynamics of the photo-excited 2D crystal. Our work provides a foundation for exploring how fs light pulses can influence phonon dynamics in materials with strong spin-lattice coupling. These results suggest that CAPs can match the magnon frequencies and show the promise of CrSBr for use in optical-to-microwave transducers and phononic devices.

43 PARTICLE ACCELERATORS↗
DOE OSTI2020

Experimental and Theoretical Studies of Ultrafast Vibrational Energy Transfer Dynamics in Energetic Materials

Energy transfer through anharmonically-coupled vibrations influences the earliest chemical steps in shockwave-induced detonation in energetic materials. A mechanistic description of vibrational energy transfer is therefore necessary to develop predictive models of energetic material behavior. We performed transient broadband infrared spectroscopy on hundreds of femtoseconds to hundreds of picosecond timescales as well as density functional theory and molecular dynamics simulations to investigate the evolution of vibrational energy distribution in thin film samples of pentaerythritol tetranitrate (PETN) , 1,3,5 - trinitroperhydro - 1,3,5 - triazine (RDX) , and 2,4,6 - triamino 1,3,5 - trinitrobenzene (TATB). Experimental results show dynamics on multiple timescales, providing strong evidence for coupled vibrations in these systems, as well as material-dependent evolution on tens to hundreds of picosecond timescales. Theoretical results also reveal pathways and distinct timescales for energy transfer through coupled vibrations in the three investigated materials, providing further insight into the mechanistic underpinnings of energy transfer dynamics in energetic material sensitivity.

36 MATERIALS SCIENCE↗
DOE OSTI2020

High-resolution analogue of time-domain phonon spectroscopy in the transmission electron microscope

Femtosecond photoexcitation of semiconducting materials leads to the generation of coherent acoustic phonons (CAPs), the behaviours of which are linked to intrinsic and engineered electronic, optical and structural properties. While often studied with pump-probe spectroscopic techniques, the influence of nanoscale structure and morphology on CAP dynamics can be challenging to resolve with these all-optical methods. Here, we used ultrafast electron microscopy (UEM) to resolve variations in CAP dynamics caused by differences in the degree of crystallinity in as-prepared and annealed GaAs lamellae. Following in situ femtosecond photoexcitation, we directly imaged the generation and propagation dynamics of hypersonic CAPs in a mostly amorphous and, following an in situ photothermal anneal, a mostly crystalline lamella. Subtle differences in both the initial hypersonic velocities and the asymptotic relaxation behaviours were resolved via construction of space-time contour plots from phonon wavefronts. Comparison to bulk sound velocities in crystalline and amorphous GaAs reveals the influence of the mixed amorphous-crystalline morphology on CAP dispersion behaviours. Further, an increase in the asymptotic velocity following annealing establishes the sensitivity of quantitative UEM imaging to both structural and compositional variations through differences in bonding and elasticity. Lastly, implications of extending the methods and results reported here to elucidating correlated electronic, optical and structural behaviours in semiconducting materials are discussed.

42 ENGINEERING↗
DOE OSTI2022

Ultrafast kinetics of the antiferromagnetic-ferromagnetic phase transition in FeRh

Understanding how fast short-range interactions build up long-range order is one of the most intriguing topics in condensed matter physics. FeRh is a test specimen for studying this problem in magnetism, where the microscopic spin-spin exchange interaction is ultimately responsible for either ferro- or antiferromagnetic macroscopic order. Femtosecond laser excitation can induce ferromagnetism in antiferromagnetic FeRh, but the mechanism and dynamics of this transition are topics of intense debates. Employing double-pump THz emission spectroscopy has enabled us to dramatically increase the temporal detection window of THz emission probes of transient states without sacrificing any loss of resolution or sensitivity. It allows us to study the kinetics of emergent ferromagnetism from the femtosecond up to the nanosecond timescales in FeRh/Pt bilayers. Our results strongly suggest a latency period between the initial pump-excitation and the emission of THz radiation by ferromagnetic nuclei.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Ultrafast Exciton Dynamics of CH 3 NH 3 PbBr 3 Perovskite Nanoclusters

Exciton dynamics of perovskite nanoclusters has been investigated for the first time using femtosecond transient absorption (TA) and time-resolved photoluminescence (TRPL) spectroscopy. The TA results show two photoinduced absorption signals at 420 and 461 nm and a photoinduced bleach (PB) signal at 448 nm. The analysis of the PB recovery kinetic decay and kinetic model uncovered multiple processes contributing to electron-hole recombination. The fast component (~8 ps) is attributed to vibrational relaxation within the initial excited state, and the medium component (~60 ps) is attributed to shallow carrier trapping. The slow component is attributed to deep carrier trapping from the initial conduction band edge (~666 ps) and the shallow trap state (~40 ps). The TRPL reveals longer time dynamics, with modeled lifetimes of 6.6 and 93 ns attributed to recombination through the deep trap state and direct band edge recombination, respectively. In conclusion, the significant role of exciton trapping processes in the dynamics indicates that these highly confined nanoclusters have defect-rich surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Fragmentation dynamics of CS 2 dications and trications following S 2p ionization

Here, we present the results from a detailed study of the fragmentation dynamics of CS$_2^{2+}$ and CS$_2^{3+}$, formed in intense femtosecond soft x-ray pulses above the sulfur 2p edge, primarily through single core photoionization from the S 2p site, and subsequent Auger–Meitner decay(s). By combining three-dimensional velocity map imaging with covariance analysis, we determine the relative momenta of the ions produced in each two- and three-body fragmentation channel, at significantly higher ion count rates than conventional coincidence measurements. We shed new light on the wide range of fragmentation channels observed from the CS 2 dication and trication, including channels that involve ionization-induced bond formation and fragmentations producing undetected neutral cofragments. In the latter case, a “native frames” approach is used to isolate contributions from concerted and sequential fragmentations and extract dynamical information about each step of a concerted fragmentation process. While dications often fragment sequentially, the trication is dominated by concerted fragmentation. The main trication fragmentation channel into S + + C + + S + can be well-approximated by classical Coulombic simulations of the ground-state geometry distribution, reflecting both the nature of the trication potential energy surface and the rapid multiple ionization prior to substantial structural dynamics. This study demonstrates ways in which fundamental insights into the fragmentation dynamics of polycations following x-ray ionization may be extracted, which will be beneficial to future studies that employ time-resolved x-ray Coulomb explosion imaging to study ultrafast photochemistry.

Allum, Felix [Deutsches Elektronen-Synchrotron (DE↗
DOE OSTI2025

Ultrafast x-ray diffraction of high-pressure phases in dynamically compressed TiO 2

Here, we investigate the high-pressure polymorphism of Ti⁢O 2 under laser-shock compression from 54(5) to 137(7) GPa using in situ femtosecond x-ray diffraction. Our results provide experimental evidence of the 𝑃⁢𝑐⁢𝑎⁢2 1 -type distorted fluorite structure formed from polycrystalline Ti⁢O 2 dynamically compressed to 54(5) GPa. Upon higher compression, we observe the direct formation of the ninefold coordinated F⁡e 2 ⁢P-type phase at 68(4) and 78(3) GPa in polycrystalline and [001]-oriented Ti⁢O 2 , respectively. This represents an unprecedented 100 GPa reduction in the shock synthesis pressure of the F⁡e 2⁢ P-type structure relative to quasihydrostatic loading conditions. On pressure release, the F⁡e 2⁢ P-type phase transforms to the α-Pb⁢O 2 structure and, at later times, reverts to rutile. Thus, the rutile →F⁡e 2⁢ P and α-Pb⁢O 2 →rutile transformations are both observed to occur on nanosecond timescales. Our results highlight the unique ability of high-strain-rate uniaxial compression to synthesize novel high-pressure phases and also indicate the importance of in situ atomic-level probes in developing pressure-temperature phase diagrams.

Crystal structures↗
DOE OSTI2022

Excited-State-Selective Ultrafast Relaxation Dynamics and Photoisomerization of trans-4,4'-Azopyridine

Here, excited-state dynamics of trans-4,4’-azopyridine in ethanol is studied using femtosecond transient absorption with 30 fs temporal resolution. Exciting the system at three different wavelengths, 460- and 290-(275) nm, to access the S 1 n,π* and S 2 π,π* electronic states, respectively, reveals a 195 cm -1 vibrational coherence, that suggests that the same mode is active in both n,π* and π,π* relaxation channels. Following S 1 -excitation, relaxation proceeds via a nonrotational pathway, where a fraction of the n,π* population is trapped in a planar minimum (lifetime, 2.1 ps), while the remaining population travels further to a second shallow minimum (lifetime, 300 fs) prior to decay into the ground state. Population of the S 2 state leads to 30-fs non-rotational relaxation with a concurrent buildup of n,π* population and nearly simultaneous formation of hot ground state species. An increase in the cis-isomer quantum yield upon π,π* vs. n,π* excitation is observed, which is opposite to trans-azobenzene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ultrafast laser-induced spin–lattice dynamics in the van der Waals antiferromagnet CoPS 3

CoPS 3 stands out in the family of the van der Waals antiferromagnets XPS 3 (X = Mn, Ni, Fe, and Co) due to the unquenched orbital momentum of the magnetic Co 2+ ions, which is known to facilitate the coupling of spins to both electromagnetic waves and lattice vibrations. Here, using a time-resolved magneto-optical pump–probe technique, we experimentally study the ultrafast laser-induced dynamics of mutually correlated spins and lattice. It is shown that a femtosecond laser pulse acts as an ultrafast heater and, thus, results in the melting of the antiferromagnetic order. At the same time, the resonant pumping of the 4 T 1g → 4 T 2g electronic transition in Co 2+ ions effectively changes their orbital momentum, giving rise to a mechanical force that moves the ions in the direction parallel to the orientation of their spins, thus generating a coherent B g phonon mode at the frequency of about 4.7 THz.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗