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DOE OSTI2023

Analytic gradients for relativistic exact-two-component equation-of-motion coupled-cluster singles and doubles method

A first implementation of analytic gradients for spinor-based relativistic equation-of-motion coupled-cluster singles and doubles method using an exact two-component Hamiltonian augmented with atomic mean-field spin–orbit integrals is reported. To demonstrate its applicability, we present calculations of equilibrium structures and harmonic vibrational frequencies for the electronic ground and excited states of the radium mono-amide molecule (RaNH 2 ) and the radium mono-methoxide molecule (RaOCH 3 ). Spin–orbit coupling is shown to quench Jahn–Teller effects in the first excited state of RaOCH 3 , resulting in a C 3v equilibrium structure. Furthermore, the calculations also show that the radium atoms in these molecules serve as efficient optical cycling centers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Mass-selected ion–molecule cluster beam apparatus for ultrafast photofragmentation studies

We describe an apparatus for investigating the excited-state dissociation dynamics of mass-selected ion–molecule clusters by mass-resolving and detecting photofragment-ions and neutrals, in coincidence, using an ultrafast laser operating at high repetition rates. The apparatus comprises a source that generates ion–molecule clusters, a time-of-flight spectrometer, and a mass filter that selects the desired anions, and a linear-plus-quadratic reflectron mass spectrometer that discriminates the fragment anions after the femtosecond laser excites the clusters. The fragment neutrals and anions are then captured by two channeltron detectors. The apparatus performance is tested by measuring the photofragments: I – , CF 3 I – , and neutrals from photoexcitation of the ion–molecule cluster CF 3 I·I – using femtosecond UV laser pulses with a wavelength of 266 nm. Here, the experimental results are compared with our ground state and excited state electronic structure calculations as well as the existing results and calculations, with particular attention to the generation mechanism of the anion fragments and dissociation channels of the ion–molecule cluster CF 3 I·I – in the charge-transfer excited state.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2026

Machine Learning–Augmented Laser-Induced Breakdown Spectroscopy for Spectral Discrimination of Iron Oxalates

Enhanced characterization and phase identification of post-PUREX Pu Oxalates (PuOXA) are pivotal for nonproliferation and pre-detonation nuclear forensics. Despite significant advances in the characterization of PuO 2 samples, little is known about the impact of both the chemical structure and oxidation states of PuOXA (i.e., Pu(III) and Pu(IV)) have on optical emission signatures. Here, we demonstrate the analytical capabilities of laser-induced breakdown spectroscopy (LIBS) applied to Fe(II) and Fe(III) oxalate samples as surrogates for PuOXA, highlighting the discriminating features in the LIBS emission spectra arising from differences in the oxidation states within mixed FeOXA samples. We report the enhancement of spectral feature selection using Principal Component Analysis (PCA), which enables the analytical superiority of machine learning algorithms such as Linear Discriminant Analysis (LDA), Quadratic Discriminant Analysis (QDA), Partial Least Squares Regression (PLSR), Support Vector Regression (SVR), and Random Forest Regression (RFR) over conventional univariate techniques for phase discrimination and chemometric analysis. Cluster analysis revealed how both matrix effects and laser ablation influence cluster separability by introducing spectral artifacts that misdirect the maximization of variance. PCA-selected emission lines were used in the regression models, demonstrating that both univariate and multivariate linear regression models (i.e., PLSR and SVR) can achieve acceptable performance, with machine learning models outperforming conventional calibration regressions. Furthermore, the application of non-linearly activated PCA-selected emission lines illustrates how simplifying the data while retaining captured variance enables the use of less complex and more computationally efficient models. Furthermore, this is particularly evident in the underperformance of RFR, which suffers from increased computational costs and overfitting owing to its high complexity.

Oxalates↗

NASA NTRS1994

Theoretical Study of Electron Scattering By Small Clusters and Adsorbates

Current interest in clusters stems from their role as novel materials as well as a possible extension of cluster results to bulk systems. Experimental investigations on clusters have been carried out using laser spectroscopy, microwave spectroscopy, heavy-particle collisions, as well as electron collisions with earlier experimental work on electron attachment and ionization having been reviewed previously. Recently, Mark and coworkers studied the decay channels of cluster ions following electron impact ionization. Rauth et al. reported the formation of the superhalogen ion SF7(-) and other nonstoichiometric cluster ions in their study of electron attachment to SF6 clusters. Kresin et al. measured the absolute electron-impact depletion cross section of metal clusters Na8, Na(20), and Na(40). They found that the inelastic scattering cross section increased with cluster size and was considerably greater than the hard sphere collision cross sections. They hypothesized that electron attachment and collision-induced fragmentation were the dominant physical processes responsible for this effect. For the two smaller clusters, they also found a sharp increase in the cross section near threshold. Most theoretical studies of clusters have been devoted to their electronic structures, vibrational relaxation, and predissociation while investigations of electron scattering from clusters has been lacking. In view of this, we recently undertook an ab initio study of electron scattering from small Be clusters and BeCO. Beryllium was chosen because it is readily amenable to ab t'nitio calculations. Moreover, the electronic structure of Be clusters has been studied extensively, showing that the Be-Be bond is relatively weak in comparison with a normal chemical bond. Our investigation focuses on how the cross sections change with cluster size and geometry. The range of energy studied, 0.05 - 5.0 eV, is chosen because of the ubiquitous resonance in the low-energy scattering of Be. Hence it can be determined if it is possible, as a consequence of the weaker bonds in the Be clusters, to identify the atomic origin of the cluster resonance.

Huo, Winifred M.↗

DOE OSTI2021

Defect Characterization Using Positron Annihilation Spectroscopy on Laser-Ablated Surfaces

In recent years, short, pulsed laser ablation has been gaining popularity for machining small-scale test geometries from bulk samples and for efficient serial sectioning. These laser-based techniques are being added to the toolbox in material science, which makes it necessary to understand the changes in the material that occur from the laser–material interaction. Positron annihilation spectroscopy is a unique, nondestructive technique to investigate small defects in materials difficult to investigate by other tools. In this work, Doppler broadening and positron lifetime annihilation spectroscopy are utilized to help quantify the damage in materials treated with short, pulsed lasers. Using a femtosecond laser on single crystal silicon, this manuscript shows that clusters of vacancy-like defects and small voids increase systematically with laser power. Lastly, the damage induced by the laser can also reach to micrometer depths.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Time-dependent equation-of-motion coupled-cluster simulations with a defective Hamiltonian

Here simulations of laser-induced electron dynamics in a molecular system are performed using time-dependent (TD) equation-of-motion (EOM) coupled-cluster (CC) theory. The target system has been chosen to highlight potential shortcomings of truncated TD-EOM-CC methods [represented in this work by TD-EOM-CC with single and double excitations (TD-EOM-CCSD)], where unphysical spectroscopic features can emerge. Specifically, we explore driven resonant electronic excitations in magnesium fluoride in the proximity of an avoided crossing. Near the avoided crossing, the CCSD similarity-transformed Hamiltonian is defective, meaning that it has complex eigenvalues, and oscillator strengths may take on negative values. When an external field is applied to drive transitions to states exhibiting these traits, unphysical dynamics are observed. For example, the stationary states that make up the time-dependent state acquire populations that can be negative, exceed one, or even complex-valued.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2004

Chemical models for simulating single-walled nanotube production in arc vaporization and laser ablation processes

Chemical kinetic models for the nucleation and growth of clusters and single-walled carbon nanotube (SWNT) growth are developed for numerical simulations of the production of SWNTs. Two models that involve evaporation and condensation of carbon and metal catalysts, a full model involving all carbon clusters up to C80, and a reduced model are discussed. The full model is based on a fullerene model, but nickel and carbon/nickel cluster reactions are added to form SWNTs from soot and fullerenes. The full model has a large number of species--so large that to incorporate them into a flow field computation for simulating laser ablation and arc processes requires that they be simplified. The model is reduced by defining large clusters that represent many various sized clusters. Comparisons are given between these models for cases that may be applicable to arc and laser ablation production. Solutions to the system of chemical rate equations of these models for a ramped temperature profile show that production of various species, including SWNTs, agree to within about 50% for a fast ramp, and within 10% for a slower temperature decay time.

Nanotubes, Carbon/chemistry↗

NASA NTRS1996

A measurement concept for hot-spot BRDFs from space

Several concepts for canopy hot-spot measurements from space have been investigated. The most promising involves active illumination and bistatic detection that would allow hot-spot angular distribution (BRDF) measurements from space in a search-light mode. The concept includes a pointable illumination source, such as a laser operating at an atmospheric window wavelength, coupled with a number of high spatial-resolution detectors that are clustered around the illumination source in space, receiving photons nearly coaxial with the reto-reflection direction. Microwave control and command among the satellite cluster would allow orienting the direction of the laser beam as well as the focusing detectors simultaneously so that the coupled system can function like a search light with almost unlimited pointing capabilities. The concept is called the Hot-Spot Search-Light (HSSL) satellite. A nominal satellite altitude of 600 km will allow hot-spot BRDF measurements out to about 18 degrees phase angle. The distributed are taking radiometric measurements of the intensity wings of the hot-spot angular distribution without the need for complex imaging detectors. The system can be operated at night for increased signal-to-noise ratio. This way the hot-spot angular signatures can be quantified and parameterized in sufficient detail to extract the biophysical information content of plant architectures.

Reflectivity↗

NASA NTRS2019

Laser Rayleigh Scattering for Flow Density and Condensation Measurements in the Supercooled Mach-14 Free-Stream at AEDC Wind Tunnel No. 9

Laser Rayleigh scattering was used to investigate clusters in the free-stream flow at Arnold Engineering Development Center’s Tunnel 9 (T9). The facility was run at Mach-14, with a pure-N2 flow medium, and at several total pressures and temperatures. Using an excimer laser operating at 248 nm, the Rayleigh instrument imaged scattering from the focused laser beam in the free-stream. As a wind-tunnel flow is accelerated, it cools and approaches the condensation boundary. As a precursor to condensation, small clusters of molecules are first formed, but the individual clusters are too small to be spatially resolved in typical images of the beam. Thus clusters effectively add a spatially smooth background signal to the pure diatomic-molecule Rayleigh signal. The main result of the present work is that clustering was not significant. After correcting for interference by small particles imbedded in the T9 flow, cluster scattering was unobservable or smaller than one standard deviation (1-sigma) of the uncertainties for almost all tunnel runs. The total light scattering level was measured to be 1.05 +/- 0.15 (1-sigma) of the expected diatomic scattering, when averaged over the entire usable data set. This result included flow conditions that were supercooled to temperatures of ~ 20 K, about 25 K below the condensation limit of ~ 45 K. Thus the Mach-14 nozzle flow is essentially cluster-free for many supercooled conditions that might be used to extend the facility operating range to larger Reynolds numbers.

Herring, Gregory C.↗

DOE OSTI2024

Double diffraction imaging of x-ray induced structural dynamics in single free nanoparticles

Abstract Because of their high photon flux, x-ray free-electron lasers (FEL) allow to resolve the structure of individual nanoparticles via coherent diffractive imaging (CDI) within a single x-ray pulse. Since the inevitable rapid destruction of the sample limits the achievable resolution, a thorough understanding of the spatiotemporal evolution of matter on the nanoscale following the irradiation is crucial. We present a technique to track x-ray induced structural changes in time and space by recording two consecutive diffraction patterns of the same single, free-flying nanoparticle, acquired separately on two large-area detectors opposite to each other, thus examining both the initial and evolved particle structure. We demonstrate the method at the extreme ultraviolet (XUV) and soft x-ray Free-electron LASer in Hamburg (FLASH), investigating xenon clusters as model systems. By splitting a single XUV pulse, two diffraction patterns from the same particle can be obtained. For focus intensities of about 2 × 10 12 W cm −2 we observe still largely intact clusters even at the longest delays of up to 650 picoseconds of the second pulse, indicating that in the highly absorbing systems the damage remains confined to one side of the cluster. Instead, in case of five times higher flux, the diffraction patterns show clear signatures of disintegration, namely increased diameters and density fluctuations in the fragmenting clusters. Future improvements to the accessible range of dynamics and time resolution of the approach are discussed.

Sauppe, M. (ORCID:0000000163123102)↗

DOE OSTI2025

Spectroscopic and Computational Studies of Spin-Orbit Coupling of Lanthanide Oxides

Spin-orbit (SO) coupling makes it possible for spin forbidden transitions or reactions within non-relativistic quantum theory feasible. Thus, quantification of such interactions has important implications in photophysics and chemical catalysis. This work aims to quantify SO interactions using lanthanide (Ln) oxides as target molecular systems. Through these systems, we examine the impact on the SO coupling by electron configurations and 4f orbital occupancies of Ln elements and sizes of the metal oxides. By examining these factors, we explore how SO coupling is affected by the number of Ln 4f electrons for a given size of molecules and if the Ln 4f orbitals remain atomic in nature in these small clusters. Ln oxides are produced in laser ablation molecular beams, identified with time-of-fight mass spectrometry, and characterized with laser spectroscopy and relativistic quantum chemical computations. Spectroscopic measurements include mass-analyzed threshold ionization (MATI), zero electron kinetic energy, and slow electron velocity-map imaging spectroscopies. Relativistic computations treat scalar relativistic corrections, electron correlations, and SO interactions. The main results are SO terms and energies of the neutral molecules and singly charged cations, ionization energies of the neutral species, metal-metal and metal-oxygen vibrational frequencies of the ions and, in some cases, neutrals as well, and charge effects on the bonding and structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1992

Diagnosis of NMOS DRAM functional performance as affected by a picosecond dye laser

A picosec pulsed dye laser beam was at selected wavelengths successfully used to simulate heavy-ion single-event effects (SEEs) in negative channel NMOS DRAMs. A DRAM was used to develop the test technique because bit-mapping capability and previous heavy-ion upset data were available. The present analysis is the first to establish such a correlation between laser and heavy-ion data for devices, such as the NMOS DRAM, where charge collection is dominated by long-range diffusion, which is controlled by carrier density at remote distances from a depletion region. In the latter case, penetration depth is an important parameter and is included in the present analysis. A single-pulse picosecond dye laser beam (1.5 microns diameter) focused onto a single cell component can upset a single memory cell; clusters of memory cell upsets (multiple errors) were observed when the laser energy was increased above the threshold energy. The multiple errors were analyzed as a function of the bias voltage and total energy of a single pulse. A diffusion model to distinguish the multiple upsets from the laser-induced charge agreed well with previously reported heavy ion data.

Kim, Q.↗

DOE OSTI2026

Pulsed laser synthesis of mesoporous metal chalcogenide thin films

Mesoporous films of the metal chalcogenide B-FeSe were grown on MgO substrates by KrF pulsed laser deposition (PLD) in an argon background. At 100 mTorr, gated intensified charge-coupled device imaging and ion probe measurements showed that the plasma plume responsible for crystal growth initially comprised three components, with distinct expansion velocities. Plume interactions with the substrate heater and ablation target gave rise to complex dynamics, including collisions between the charged leading edge—rebounding between the substrate and the target—and slower-moving species in the plume interior. Film growth was dominated by species with kinetic energies ≤0.5 eV/atom. X-ray reflectivity revealed that films grown in this environment—with a substrate temperature of 350 ° C, a laser fluence of 1.0 J cm −2 , and a 7.5 mm 2 spot area—formed a porous framework with 15% porosity. Atomic force microscopy showed surface features that suggest pore sizes below 100 nm. X-ray diffraction indicated that the porous films were epitaxial with respect to the substrate and likely grew by oriented-attachment of gas-phase molecular clusters or very small nanoparticles, in contrast to the conventional epitaxy of vacuum films from atomic constituents. The in-plane orientation of the mesoporous films was B-FeSe [100]||[110] MgO, attributed to the soft landing of pre-formed crystallites on the MgO substrates, where protruding Se rows of B-FeSe aligned with corrugations of the MgO surface. In conclusion, this work implies that growth of candidate electrocatalyst materials by PLD in inert gas background may allow mesoporous frameworks with a single crystallographic orientation that expose specific crystal facets for electrochemical reactions and active site engineering.

cluster epitaxy↗

NASA NTRS2012

Rayleigh Scattering Density Measurements, Cluster Theory, and Nucleation Calculations at Mach 10

In an exploratory investigation, quantitative unclustered laser Rayleigh scattering measurements of density were performed in the air in the NASA Langley Research Center's 31 in. Mach 10 wind tunnel. A review of 20 previous years of data in supersonic and Mach 6 hypersonic flows is presented where clustered signals typically overwhelmed molecular signals. A review of nucleation theory and accompanying nucleation calculations are also provided to interpret the current observed lack of clustering. Data were acquired at a fixed stagnation temperature near 990Kat five stagnation pressures spanning 2.41 to 10.0 MPa (350 to 1454 psi) using a pulsed argon fluoride excimer laser and double-intensified charge-coupled device camera. Data averaged over 371 images and 210 pixels along a 36.7mmline measured freestream densities that agree with computed isentropic-expansion densities to less than 2% and less than 6% at the highest and lowest densities, respectively. Cluster-free Mach 10 results are compared with previous clustered Mach 6 and condensation-free Mach 14 results. Evidence is presented indicating vibrationally excited oxygen and nitrogen molecules are absorbed as the clusters form, release their excess energy, and inhibit or possibly reverse the clustering process. Implications for delaying clustering and condensation onset in hypersonic and hypervelocity facilities are discussed.

Balla, R. Jeffrey↗

DOE OSTI2023

Real-Time Diagnostics of 2D Crystal Transformations by Pulsed Laser Deposition: Controlled Synthesis of Janus WSSe Monolayers and Alloys

Energetic processing methods such as hyperthermal implantation hold special promise to achieve the precision synthesis of metastable two-dimensional (2D) materials such as Janus monolayers; however, they require precise control. Here, we report a feedback approach to reveal and control the transformation pathways in materials synthesis by pulsed laser deposition (PLD) and apply it to investigate the transformation kinetics of monolayer WS 2 crystals into Janus WSSe and WSe 2 by implantation of Se clusters with different maximum kinetic energies (<42 eV/Se-atom) generated by laser ablation of a Se target. Real-time Raman spectroscopy and photoluminescence are used to assess the structure, composition, and optoelectronic quality of the monolayer crystal as it is implanted with well-controlled fluxes of selenium for different kinetic energies that are regulated with in situ ICCD imaging, ion probe, and spectroscopy diagnostics. First-principles calculations, XPS, and atomic-resolution HAADF STEM imaging are used to understand the intermediate alloy compositions and their vibrational modes to identify transformation pathways. The real-time kinetics measurements reveal highly selective top-layer conversion as WS 2 transforms through WS 2(1–x) Se 2x alloys to WSe 2 and provide the means to adjust processing conditions to achieve fractional and complete Janus WSSe monolayers as metastable transition states. The general approach demonstrates a real-time feedback method to achieve Janus layers or other metastable alloys of the desired composition, and a general means to adjust the structure and quality of materials grown by PLD, addressing priority research directions for precision synthesis with real-time adaptive control.

2D materials↗

DOE OSTI2020

Photodissociation and Theory to Investigate Uranium Oxide Cluster Cations

Uranium oxide cluster cations of the form U n O m + are produced by laser vaporization of a depleted uranium rod in a pulsed supersonic expansion. Ions are mass-analyzed and mass-selected with a time-of-flight spectrometer and studied with UV laser multiphoton dissociation. Cations of the stoichiometry UO 2 (UO 3 ) n + were observed as photofragments from all photodissociated cluster cations. (UO 3 ) n + clusters were also observed to result from dissociation of larger (UO 3 ) n + clusters, with UO 3 neutral as a common leaving group. Electronic structure calculations were used to investigate the stability of the prominent uranium oxide cluster cations using density functional theory (DFT) with the hybrid B3LYP exchange-correlation functional and at the CCSD(T) level and cc-pVnZ-PP basis sets (n = D,T), including diffuse orbitals as computational expense and availability permitted. Clustering energies, relative energies and dissociation energies of the cations are reported. The lowest energy neutral (UO 3 ) n clusters up to n = 3 are rings, n = 4 and 5 are chains with very low energy rings, and n = 6 is 3D. Finally, the lowest energy structures for UO 2 (UO 3 ) n + are composed of uranyl-like UO 2 + units bound by bridging oxygens to other UO 2 2+ units for n = 2 and 3, and for n = 4 a more complex 3D structure is predicted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Statistical analysis of spatial distribution of pores in metal additive manufacturing

We report mechanical properties of additively manufactured parts are sensitive to the presence of pores form during the manufacturing process. The impact of pores on the mechanical performance has been investigated extensively with respect to different parameters, such as pore volume fraction, shape, and size. However, statistical investigations focusing on the relationships between the spatial distribution of pores and process parameters; and consequently, the performance of the manufactured parts are scattered and limited. Also, these sparse investigations usually suffer from an ambiguous definition of terminologies. For instance, the required criteria to consider a point pattern as complete spatial randomness (CSR) are generally not clarified. Moreover, no numerical formalism is yet developed to show how much the observed spatial results are statistically significant. To address these shortcomings, the statistical definition of CSR in a point pattern and the procedure to quantitatively determine the deviation of a pattern from CSR were discussed. The explained statistical approach was used to investigate the effect of scanning speed parameter on the spatial distribution of gas pores in laser powder bed fusion manufactured stainless steel parts. Furthermore, and to highlight the impact of the spatial distribution of pores on mechanical properties, fatigue performances of parts with clustered and randomly distributed pores were simulated by finite element analysis. It is shown that by reducing the scanning speed, the spatial distribution of gas pores deviated more from CSR, and correspondingly fatigue performance deteriorated.

36 MATERIALS SCIENCE↗

NASA NTRS1991

Study of cluster formation and its effects on Rayleigh and Raman scattering measurements in a Mach 6 wind tunnel

Using a frequency-doubled Nd-YAG pulsed laser and a single-intensified CCD camera, Rayleigh scattering measurements have been performed to study the cluster formation in a Mach 6 wind tunnel at NASA Langley Research Center. These studies were conducted both in the free stream and in a model flow field for various flow conditions to gain an understanding of the dependence of the Rayleigh scattering (by clusters) on the local pressures and temperatures in the facility. Using the same laser system, simultaneous measurements of the local temperature have also been performed using the rotational Raman scattering of molecular nitrogen and determined the densities of molecular oxygen and nitrogen by using the vibrational Raman scattering from these species. Quantitative results are presented in detail with emphasis on the applicability of the Rayleigh scattering for obtaining quantitative measurements of molecular densities both in the free stream and in the model flow field.

Shirinzadeh, B.↗