Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ELECTRON TRANSITION”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Spectroscopic characterization of a new Re(i) tricarbonyl complex with a thiosemicarbazone derivative: towards sensing and electrocatalytic applications

This work describes the preparation of a new thiosemicarbazone derivative, (Z)- N -ethyl-2-(6-oxo-1,10-phenanthrolin-5(6 H )-ylidene)hydrazinecarbothioamide (phet) and its respective Re( I ) tricarbonyl chloro complex, fac -[ReCl(CO) 3 (phet)]. The spectroscopic, photophysical and electrochemical properties of the new complex were fully investigated through steady state and time-resolved techniques along with computational calculations. In fac -[ReCl(CO) 3 (phet)], the new ligand is coordinated to the metal center through the pyridyl rings of the phenanthroline moiety. The unbound electron pairs in the S atom of the bending thiosemicarbazone group induce new low energy lying electronic transitions. Consequently, enhanced visible light absorption up to 550 nm is observed in acetonitrile due to the overlap between MLCT Re→phet and IL phet(n→π*) transitions. The absorption bands and emission quantum yields of fac -[ReCl(CO) 3 (phet)] are sensitive to proton concentration due to an acid-basic equilibrium in the N atoms of the thiosemicarbazone. Proton dissociation constants of 10.0 ± 0.1 and 11.4 ± 0.2 were determined respectively for the ground and excited states of the new complex. Spectral changes could also be observed in the presence of Zn 2+ cations which can be further explored for sensing applications. The electrochemical behavior of the new complex was studied in detail, revealing up to four one electron reduction processes in the range from 0 to -2.4 V vs. Fc + /Fc. With support of DFT calculations, the first three processes are ascribed to the reduction of the coordinated phet ligand followed by the Re I/0 reduction and consequent Cl - release. Furthermore, the new complex was able to act as an electrocatalyst for CO 2 reduction into CO ( E onset = -1.92 V vs. Fc + /Fc), with a turnover frequency of 2.81 s -1 and turnover number of 24 ± 1 in anhydrous acetonitrile, being the first Re( I ) tricarbonyl complex with a thiosemicarbazone derivative described for this goal. The detailed characterization carried out here can drive the development of new Re( I )-thiosemicarbazone derivatives for different applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Directly measuring the structural transition pathways of strain-engineered VO 2 thin films

Epitaxial films of vanadium dioxide (VO 2 ) on rutile TiO 2 substrates provide a means of strain-engineering the transition pathways and stabilizing of the intermediate phases between monoclinic (insulating) M1 and rutile (metal) R end phases. In this work, we investigate structural behavior of epitaxial VO 2 thin films deposited on isostructural MgF 2 (001) and (110) substrates via temperature-dependent Raman microscopy analysis. The choice of MgF 2 substrate clearly reveals how elongation of V–V dimers accompanied by the shortening of V–O bonds triggers the intermediate M2 phase in the temperature range between 70–80 °C upon the heating–cooling cycles. Consistent with earlier claims of strain-induced electron correlation enhancement destabilizing the M2 phase our temperature-dependent Raman study supports a small temperature window for this phase. The similarity of the hysteretic behavior of structural and electronic transitions suggests that the structural transitions play key roles in the switching properties of epitaxial VO 2 thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2021

How the Size and Density of Charge-Transfer Excitons Depend on Heterojunction’s Architecture

We have characterized the size, intensity, density, and distribution of charge-transfer (CT) excitons as a function of the acceptor–donor architecture of prototypical organic interfaces. This characterization was done by computational analysis of 17 models of varying numbers, positions, and orientations of the donor and acceptor molecules. The models’ building blocks were phenyl-C61-butyric acid methyl ester (PCBM) fullerene acceptors and dual-band donor polymers composed of thiophene, benzothiadiazole, and benzotriazole subunits. The electronic structure of the donor–acceptor complexes was computed with the time-dependent long-range-corrected density-functional tight-binding method and analyzed with the fragment-based one-electron transition density matrix. In all models, the complexes with edge-on orientation have denser spectra of low-energy CT states lying below the absorption bands compared to the complexes with face-on orientation. This CT-state distribution in edge-on complexes provides a gate to efficiently populate cold CT excitons. Moreover, the cold CT excitons have a higher degree of charge separation in the edge-on than in the face-on complexes. The CT amount and the CT exciton size generally increase with the energy of the CT states, although the electron remains localized on a single molecule in cold CT states. Delocalization over two PCBM molecules was observed for high-energy CT states. The exciton size also depends on the orientation. Larger excitons are produced by the delocalization of the electrons perpendicularly to the interface. When the delocalization is parallel, the smaller electron–hole distances yield moderately sized CT excitons.

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

Nanomolar Sensitivity Chirality Transfer from Designed Helical Repeat Proteins to Achiral CdS Nanorods

Bridging chirality across length scales with inorganic− organic hybrid materials is a rapidly expanding area of research. Here, we establish asymmetry at CdS nanorod (NR) interfaces using a designed helical repeat protein bearing four cysteine residues (DHR- 4Cys). Hydrophobic NRs are transferred into water with glycine, and then glycine is displaced by DHR-4Cys, leveraging the thiophilicity of cadmium. Circular dichroism (CD) in the visible, coincident with CdS electronic transitions, reveals a chiral DHR-4Cys:CdS interface. Here, the dissymmetry factor [g-factor = 4.5 × 10 −4 (short NRs) and 5.0 × 10 −4 (long NRs)] is weakly dependent on the NR length, and CD persists at nanomolar protein loadings. Additionally, control experiments demonstrate that DHR-4Cys:CdS NR chirality is dictated by the local coordination of Cys with no significant contribution from the chiral secondary structure of the protein (g-factors of short and long Cys:CdS NRs are 4.8 × 10 −4 and 4.0 × 10 −4 , respectively). Together with far-UV CD and transmission electron microscopy, which provide evidence of preserved protein structure, these results provide the first demonstration that a structurally defined protein can induce chirality in CdS nanocrystals while maintaining protein structure at biologically relevant concentrations.

Cadmium sulfide↗
DOE OSTI2021

Opacity Table Generation

Radiation opacity is a key property of material systems which describes the absorption and scattering of photons. Such processes are an important part of energy transport, diagnostics, and astrophysical phenomena. Recent experiments in iron opacity and continuum lowering have sparked renewed interest in and careful vetting of opacity models. Even within the local thermodynamic equilibrium approximation, opacity varies over a large parameter space: material, temperature, density, and energy. Opacity tables that span wide regimes of this parameter space are of prime importance to radiation-hydrodynamics codes. Accurate opacity calculations cannot be achieved inline during a radiation hydrodynamics simulation since they involve accounting for all possible electron transitions of all important atomic states of a thermal ensemble. Livermore’s current framework utilizes precalculated tables at many densities, temperatures, and energies. Last year, the opacity theory team completed an L2 milestone concerning the development of a new code, Opus, which served the dual purpose of creating a modern code infrastructure and version control as well as the basis for training new members of that team, a critical need as key members near or are passed retirement. For the current L2 milestone, we exercised and validated Opus on three elements: boron, carbon, and nitrogen, which have few enough electrons to allow a careful convergence study over many input parameters. Here, we report on the production of new tables, show their convergence with respect to important parameters, state some of their limitations, and document a mostly automated production process. In this section, we address the milestone completion criteria, found on the title page and the subsection headings. In section 2, we validate Opus against Tycho and compare with TabOp and Atomic. Section 3 details some of the physics implemented in Opus and relevant to this report. We then cover details of the density-temperature grid in section 4 and do a spectral comparison between different parameter settings and different codes in section 5. After summarizing these results in section 6, we give instructions how to run the opacity table scripts in appendix A and document the scripts and input/output files in appendix B.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

High-resolution spectroscopy of neutral Yb atoms in a solid Ne matrix

Here, we present an experimental and theoretical study of the absorption and emission spectra of Yb atoms in a solid Ne matrix at a resolution of 0.025 nm. Five absorption bands were identified as due to transitions from the 4 f 14 5 d 0 6 s 2 1 S 0 ground-state configuration to 4 f 14 5 d 0 6 s 6 p and 4 f 13 5 d 1 6 s 2 configurations. The two lowest-energy bands were assigned to outer-shell transitions to 6 s 6 p 3 P 1 and 1 P 1 atomic states and displayed the structure of a broad doublet and an asymmetric triplet, respectively. The remaining three higher-frequency bands were assigned to inner-shell transitions to distinct J = 1 states arising from the 4 f 13 5 d 1 6 s 2 configuration and were highly structured with narrow linewidths. A classical simulation was performed to identify the stability and symmetry of possible trapping sites in the Ne crystal. It showed that the overarching 1 + 2 structure of the high-frequency bands could be predominantly ascribed to crystal-field splitting in the axial field of a 10-atom vacancy of C 4 v symmetry. Their prominent substructures were shown to be manifestations of phonon sidebands associated with the zero-phonon lines on each crystal-field state. Unprecedented for a metal–rare-gas system, resolution of individual phonon states on an allowed electronic transition was possible under excitation spectroscopy which reflects the semiquantum nature of solid Ne. In contrast to the absorption spectra, emission spectra produced by steady-state excitation into the 1 P 1 absorption band consisted of simple, unstructured fluorescence bands.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Spectrally filtered ps–ns emission dynamics of atmospheric-pressure nanosecond pulsed plasmas

The temporal dynamics of atmospheric-pressure nanosecond pulsed plasma discharges in a pin-to-pin electrode configuration are studied using streak-camera line imaging of the interelectrode gap with a time resolution as short as ~25 ps. Discharge emission initiates homogeneously throughout the interelectrode gap with no detectable streamer propagation and then temporally decays in two distinct phases. Plasma emission bands attributed to various electronic transitions are tracked for single discharges in air and N 2 . Spectral filtering of the excited molecular states reveals that the N 2 (C–B) and N 2 (B–A) emission bands evolve in distinct early and late phases, respectively, with a time separation of ~15–20 ns. Furthermore, significant differences in the temporal dynamics of plasma discharges in air and N2 are observed. High levels of excited-state atomic oxygen and NO appear after the initial decay of the N 2 (C) state and coincide primarily with the latter phases of plasma evolution in air environments. From temporal traces of discharge emission, the formation and relaxation timescales of the electronically excited states of N 2 are quantified in pure N2 and air environments with sub-nanosecond resolution. The streak-OES (optical emission spectroscopy) technique enables quantitative time-resolved studies of key chemical species for model validation in ultra-short-pulsed plasmas.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

6 nm super-resolution optical transmission and scattering spectroscopic imaging of carbon nanotubes using a nanometer-scale white light source

Abstract Optical transmission and scattering spectroscopic microscopy at the visible and adjacent wavelengths denote one of the most informative and inclusive characterization methods in material research. Unfortunately, restricted by the diffraction limit of light, it cannot resolve the nanoscale variation in light absorption and scattering, diagnostics of the local inhomogeneity in material structure and properties. Moreover, a large quantity of nanomaterials has anisotropic optical properties that are appealing yet hard to characterize through conventional optical methods. There is an increasing demand to extend the optical hyperspectral imaging into the nanometer length scale. In this work, we report a super-resolution hyperspectral imaging technique that uses a nanoscale white light source generated by superfocusing the light from a tungsten-halogen lamp to simultaneously obtain optical transmission and scattering spectroscopic images. A 6-nm spatial resolution in the visible to near-infrared wavelength regime (415–980 nm) is demonstrated on an individual single-walled carbon nanotube (SW-CNT). Both the longitudinal and transverse optical electronic transitions are measured, and the SW-CNT chiral indices can be identified. The band structure modulation in a SW-CNT through strain engineering is mapped.

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

Elucidating the Role of Hydrogen Bonding in the Optical Spectroscopy of the Solvated Green Fluorescent Protein Chromophore: Using Machine Learning to Establish the Importance of High-Level Electronic Structure

Hydrogen bonding interactions with chromophores in chemical and biological environments play a key role in determining their electronic absorption and relaxation processes, which are manifested in their linear and multidimensional optical spectra. For chromophores in the condensed phase, the large number of atoms needed to simulate the environment has traditionally prohibited the use of high-level excited-state electronic structure methods. By leveraging transfer learning, we show how to construct machine-learned models to accurately predict the high-level excitation energies of a chromophore in solution from only 400 high-level calculations. Here, we show that when the electronic excitations of the green fluorescent protein chromophore in water are treated using EOM-CCSD embedded in a DFT description of the solvent the optical spectrum is correctly captured and that this improvement arises from correctly treating the coupling of the electronic transition to electric fields, which leads to a larger response upon hydrogen bonding between the chromophore and water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Zinc–hydrogen and zinc–iridium pairs in β-Ga 2 O 3

Zinc-doped monoclinic gallium oxide (β-Ga 2 O 3 :Zn) has semi-insulating properties that could make it a preferred material as a substrate for power devices. In this work, infrared and UV/Visible spectroscopy were used to investigate the defect properties of bulk β-Ga 2 O 3 :Zn crystals. As-grown crystals contain a single O-H stretching mode at 3486.7 cm -1 due to a neutral ZnH complex. A deuterium-annealed sample displays the corresponding O-D stretching mode at 2582.9 cm -1 , confirming the O-H assignment. A strong Ir 4+ electronic transition at 5147.6 cm -1 is also observed, along with sidebands attributed to ZnIr pairs. These sidebands show distinct differences compared with Mg-doped samples; most importantly, several peaks are attributed to Ir 4+ paired with a Zn on the tetrahedral Ga(I) site. Annealing under an oxygen atmosphere produced insulating material with a resistance above 1 TΩ.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Charge-transfer-enhanced d – d emission in antiferromagnetic NiPS3

The d electron plays a significant role in determining and controlling the properties of magnetic materials. However, the d electron transitions, especially d–d emission, have rarely been observed in magnetic materials due to the forbidden selection rules. Here, we report an observation of d–d emission in antiferromagnetic nickel phosphorus trisulfides (NiPS3) and its strong enhancement by stacking it with monolayer tungsten disulfide (WS2). We attribute the observation of the strong d–d emission enhancement to the charge transfer between NiPS3 and WS2 in the type-I heterostructure. The d–d emission peak splits into two peaks, D1 and D2, at low temperature below 150 K, from where an energy splitting due to the trigonal crystal field is measured as 105 meV. Moreover, we find that the d–d emissions in NiPS3 are nonpolarized lights, showing no dependence on the zigzag antiferromagnetic configuration. These results reveal rich fundamental information on the electronic and optical properties of emerging van der Waals antiferromagnetic NiPS3.

Physics↗
DOE OSTI2023

X-ray induced electron and ion fragmentation dynamics in IBr

Characterization of the inner-shell decay processes in molecules containing heavy elements is key to understanding x-ray damage of molecules and materials and for medical applications with Auger-electron-emitting radionuclides. The 1s hole states of heavy atoms can be produced by absorption of tunable x rays and the resulting vacancy decays characterized by recording emitted photons, electrons, and ions. The 1s hole states in heavy elements have large x-ray fluorescence yields that transfer the hole to intermediate electron shells that then decay by sequential Auger-electron transitions that increase the ion’s charge state until the final state is reached. In molecules, the charge is spread across the atomic sites, resulting in dissociation to energetic atomic ions. We have used x-ray/ion coincidence spectroscopy to measure charge states and energies of Iq+ and Brq′+ atomic ions following 1s ionization at the I and Br K-edges of IBr. We present the charge states and kinetic energies of the two correlated fragment ions associated with core-excited states produced during the various steps of the cascades. Here, to understand the dynamics leading to the ion data, we develop a computational model that combines Monte-Carlo/Molecular-Dynamics (MC/MD) simulations with a classical over-the-barrier model to track inner-shell cascades and redistribution of electrons in valence orbitals and nuclear motion of fragments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Transient absorption spectroscopy to explore cellular pathways to photobiomodulation

Photobiomodulation (PBM) describes the use of low irradiance light in the red to near-infrared wavelength range to stimulate biological effects in tissue, and many biological and spectroscopic techniques are used to study PBM. However, these techniques focus on the products or downstream effects rather than the electronic transitions that initiate the PBM processes. This study presents a novel approach to studying low irradiance light exposures on individual proteins and/or protein complexes by combining a continuous wave (CW) laser diode with femtosecond transient absorption spectroscopy (TAS), coined here as CW-TAS, and tests the system on reduced cytochrome c (Cyt c) for proof of principle. TAS was conducted using a 532-nm excitation pump beam and a 350-600 nm supercontinuum probe. In this work, CW laser diodes with wavelengths of 450 nm, 635 nm, and 808 nm were interchangeably fiber coupled into the HELIOS Fire. Samples of Cyt c were tested by TAS using a pump power of 15 µW, both with and without CW exposure. CW exposures were carried out with irradiances of 1.60 and 3.20 mW/cm 2 , except for 808 nm, which was only tested at 1.60 mW/cm 2 . Both kinetic and global analyses were performed on the TAS data and the time constants for sets with and without CW exposures were compared. The TAS data for Cyt c with the full dosage of CW exposures did not alter the TAS data distinguishably from the control data. No new electronic transient signals were observed beyond the background when testing Cyt c with the CW exposures. Kinetic analysis confirmed that existing transients did not deviate beyond uncertainty. Global time constants for Cyt c were calculated to be 0.25 ± 0.03 ps and 5.1 ± 0.3 ps for the control study, and the time constants for the CW exposed Cyt c were not significantly different. This study concludes that CW irradiation, at doses delivered, does not alter the transient absorption data of Cyt c. The CW-TAS method provides a new tool for studying PBM effects in other proteins and protein complexes, such as Complex IV, in future studies.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Electronic excitations of α - Fe 2 O 3 heteroepitaxial films measured by resonant inelastic x-ray scattering at the Fe L edge

Resonant inelastic x-ray scattering (RIXS) spectra of hematite (α-Fe 2 O 3 ) were measured at the Fe L 3 edge for heteroepitaxial thin films which were undoped and doped with 1% Ti, Sn, or Zn, in the energy-loss range in excess of 1 eV to study electronic transitions. The spectra were measured for several momentum transfers q, conducted at both low temperature (T=14 K) and room temperature. While we cannot rule out dispersive features possibly owing to propagating excitations, the coarse envelopes of the general spectra did not appreciably change shape with q, implying that the bulk of the observed L-edge RIXS intensity originates from (mostly) nondispersive ligand field excitations. Summing the RIXS spectra over q and comparing the results at T=14 K to those at T=300 K revealed pronounced temperature effects, including an intensity change and energy shift of the ≈1.4 eV peak, a broadband intensity increase of the 3-4 eV range, and higher energy features. The q-summed spectra and their temperature dependencies are virtually identical for nearly all of the samples with different dopants, save for the temperature dependence of the Ti-doped sample's spectrum, which we attribute to being affected by a large number of free charge carriers. Comparing with magnetization measurements for different temperatures and dopings likewise did not show a clear correlation between the RIXS spectra and the magnetic ordering states. To clarify the excited states, we performed spin multiplet calculations which were in excellent agreement with the RIXS spectra over a wide energy range and provide detailed electronic descriptions of the excited states. Furthermore, the implications of these findings to the photoconversion efficiency of hematite photoanodes is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Low-Lying Excited States of Linear All- Trans Polyenes: Insights from Analytic Gradient and Nonadiabatic Coupling Calculations Based on Multireference Configuration Interaction

Polyenes serve as a rigorous test for theoretical models and electronic structure methods, playing a key role in advancing computational and theoretical chemistry. Here, we present a high-level theoretical investigation of linear, all-trans polyenes using energy gradients and nonadiabatic coupling vectors based on an MR-CISD wave function to describe electronic transitions involving the ground state (1 1 A g – ) and three low-lying excited states (2 1 A g – , 1 1 B u + , and 2 1 B u – ) of hexatriene, octatetraene, and decapentaene. This approach enables accurate evaluation of both adiabatic and vertical excitation and emission energies, yielding results in excellent agreement with experiment, as well as locating minima on the crossing seam between adiabatic states. Our results show that vertical excitation energies to the 1 1 B u + state are blue-shifted by 0.2–0.3 eV relative to the experimental absorption maximum, whereas the vertical emission energy from the 2 1 A g – state is red-shifted by ∼0.2 eV relative to the experimental emission maximum. Upon relaxation from the Franck–Condon geometry, the 2 1 A g – state stabilizes by around 1 eV, compared to 0.2–0.3 eV for the 1 1 B u + state. An analysis of the S 1 /S 0 crossing seam in hexatriene shows that its minimum involves asymmetric backbone deformations and provides an efficient channel for ultrafast internal conversion to the ground state, consistent with the absence of detectable fluorescence in this molecule. These results demonstrate the power of analytic gradients and nonadiabatic coupling vectors based on an MR-CISD wave function for accurately characterizing the electronic structure and photophysics of polyenes.

Excited states↗
DOE OSTI2023

Electronic spectroscopy and ionization potentials for YbOH and YbOCH 3

The polyatomic molecules YbOH and YbOCH 3 have been recognized as being of potential value for spectroscopic experiments that explore charge-parity and time reversal symmetry violation effects. These measurements require very high precision, which, in turn, will necessitate that the molecules be manipulated at ultra-cold temperatures. Both YbOH and YbOCH 3 have electronic transitions that appear suitable for laser cooling ($\tilde{A}$ 2 Π 1/2 -$\tilde{X}$ 2 Σ + and $\tilde{A}$2E 1/2 -$\tilde{X}$ 2 A 1 , respectively) but the currently available spectroscopic data is not sufficient to determine the extent to which population leaks may compromise the optical cooling processes. A further complication is that the quantum states of interest for these measurements will need to be selectively populated. The $\tilde{A}$-$\tilde{X}$ band systems of both YbOH and YbOCH 3 show evidence of vibronic perturbations, such that there are unassigned vibronic features at energies that are just above the origin bands. Here, in the present study we have recorded spectra for the $\tilde{A}$ 2 Π 1/2 -$\tilde{X}$ 2 Σ + transition of jet-cooled YbOD to facilitate the vibronic assignments. In addition, spectra for the $\tilde{B}$ 2 Σ + - $\tilde{X}$ 2 Σ + transition of YbOH were recorded, establishing the origin band at 20473.8 cm -1 . Previously, the reaction of Yb with CH 3 OH has been used to generate gas-phase YbOCH 3 . As this reaction also yields YbOH, there have been complications in spectroscopic studies of YbOCH 3 due to overlap of the $\tilde{A} -\tilde{X}$ band systems. To identify specific regions of overlap, resonantly enhanced two-photon ionization spectra were recorded using mass-resolved detection of the YbOH + and YbOCH 3 + ions. These data confirmed the overlap of vibronic bands near 17640 and 17680 cm -1 . Two-photon ionization spectroscopy also provided accurate ionization energies of IE(YbOH)=45788(10) and IE(YbOCH 3 )=45283(10) cm -1 . The IE for YbOH is relevant to problems encountered in previous attempts to determine the bond dissociation energy of YbOH + .

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

Experimental validation of a collision-radiation dataset for molecular hydrogen in plasmas

Quantitative spectroscopy of molecular hydrogen has generated substantial demand, leading to the accumulation of diverse elementary process data encompassing radiative transitions, electron-impact transitions, predissociations, and quenching. However, their rates currently available are still sparse, and there are inconsistencies among those proposed by different authors. In this study, we demonstrate an experimental validation of such a molecular dataset by composing a collisional-radiative model (CRM) for molecular hydrogen and comparing experimentally obtained vibronic populations across multiple levels. From the population kinetics of molecular hydrogen, the importance of each elementary process in various parameter space is studied. In low-density plasmas (electron density ne≲1017 m−3) the excitation rates from the ground states and radiative decay rates, both of which have been reported previously, determine the excited state population. The inconsistency in the excitation rates affects the population distribution the most significantly in this parameter space. However, in higher density plasmas (ne≳1018 m−3), the excitation rates from excited states become important, which have never been reported in the literature, and may need to be approximated in some way. In order to validate these molecular datasets and approximated rates, we carried out experimental observations for two different hydrogen plasmas; a low-density radio frequency heated plasma (ne≈1016 m−3) and the Large Helical Device (LHD) divertor plasma (ne≳1018 m−3). The visible emission lines from EF1Σg+, HH¯1Σg+, D1Πu±, GK1Σg+, I1Πg±, J1Δg±, h3Σg+, e3Σu+, d3Πu±,g3Σg+, i3Πg±, and j3Δg± states were observed simultaneously and their population distributions were obtained from their intensities. We compared the observed population distributions with the CRM prediction, in particular the CRM with the rates compiled by Janev et al., Miles et al., and those calculated with the molecular convergent close-coupling (MCCC) method. The MCCC prediction gives the best agreement with the experiment, particularly for the emission from the low-density plasma. However, the population distribution in the LHD divertor shows a worse agreement with the CRM than those from low-density plasma, indicating the necessity of the precise excitation rates from excited states. We also found that the rates for the electron attachment is inconsistent with experimental results. This requires further investigation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Capturing Ring Opening in Photoexcited Enolic Acetylacetone upon Hydrogen Bond Dissociation by Ultrafast Electron Diffraction

Photoinduced biological and chemical reactions are often based on key structural transformations of a molecule driven across multiple electronic states. Acetylacetone (AcAc) is a prototypical system for complex chemical pathways involving several conical intersections (CI) and singlet–triplet intersystem crossings (ISC) characterized by distinct geometries. In the gas phase, AcAc is predominantly in a planar ring-like enolic form stabilized by a strong intramolecular O–H···O hydrogen bond. Following excitation into the S 2 (ππ*) state at 266 nm, acetylacetone undergoes rapid internal conversion followed by intersystem crossing. Such relaxation pathways are associated with structural changes including ring opening, deplanarization, and bond elongation. In this work, ultrafast electron diffraction (UED) at the SLAC MeV-UED setup is employed as a direct structural probe with a time resolution of 160 fs. Together with trajectory surface hopping simulations, analysis of the UED data provides a new perspective on the early time nuclear dynamics in acetylacetone. Specifically, AcAc is observed to undergo ring opening, deplanarization, and bond elongation all within the first 700 fs after photoexcitation. The monitored dynamics is associated mainly with the nuclear motion on the S 1 potential energy surface, formed after very rapid transfer from S 2 to S 1 , allowing AcAc to reach the conical intersection to intersystem crossing. Such time scales of nuclear motion are contrasted with the time scales of electronic transitions in AcAc that were previously characterized with spectroscopic methods, specifically internal conversion (<100 fs) and intersystem crossing (∼1.5 ps).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗