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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.

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185 records · Page 11

Characterizing Ultrafast Intersystem Crossing Pathways in Molecular Pt Dimers Using Time-Resolved Wide-Angle X-ray Scattering

Vibronic coupling between transition metal charge transfer states is a potential mechanism for enhancing the intersystem crossing (ISC) rate. Vibronic coupling-driven ISC has been observed in Pt­(II) dimer complexes, where the trajectory across excited-state pathways is tuned by atomic displacements via Pt–Pt stretching vibrations. Time-resolved wide-angle X-ray scattering (TR-WAXS) was utilized to quantify the Pt–Pt contraction following metal–metal-to-ligand charge transfer (MMLCT) excitation in Pt dimers with different bridging ligands. Both complexes exhibit Pt–Pt bond formation with a decrease in Pt–Pt distance of ∼ 0.25 Å and coherent vibrational wavepackets (CVWPs) encoded in the Pt–Pt contraction of both dimers. However, the complexes exhibit different time-dependent evolution of their CVWPs. Analysis of interference patterns between different CVWPs is used to track the trajectory across the excited-state surfaces. Furthermore, this work demonstrates that the interference between CVWPs in ultrafast TR-WAXS encodes indirect information regarding electronic excited-states to reveal the Pt dimer bridge-dependent ISC mechanism.

Computational chemistry↗

New Dimensions in the Theory of Excited States and X-ray Spectra (Final Report)

This Final Technical Report briefly summarizes the achievements during the lifetime of our DOE BES grant DE-FG02-97ER45623. The long-term goal of this project has been the development of quantitative theories of the interaction between radiation and matter, with a focus on x-ray spectroscopies. X-ray spectra have long been among the most important probes of atomic-scale structure and properties of matter, ranging from atoms and molecular systems to condensed matter and exotic states. These spectroscopies are widely used in investigations at the major DOE synchrotron x-ray facilities and related centers world-wide. In addition to fundamental theory, a major goal of our project has been the development of computational software that implements the theory for calculations of x-ray spectra of various materials throughout the periodic table. Due to the complex nature of x-ray spectra, quantitative theory is essential for its interpretation. The theory is challenging since it involves excited state electronic structure and many-body correlation effects that go beyond independent particle approximations like DFT or Hartree-Fock. Moreover, the experimental investigations typically involve a broad range of energy, time, and temperature scales, from the UV-Vis to hard x-ray energies of order 10 4 eV, and temperatures T from ambient up to the warm-dense-matter regime where the Fermi energy kBTF is of order a few eV, i.e., temperatures of order 105 Kelvin. This broad range of experimental conditions has fostered many novel theoretical approaches and computational techniques, many of which we have developed systematically over the duration of the grant. In contrast to the traditional wave-function approach of quantum theory and electronic structure methods, our theoretical approach is based on modern Green's function techniques. This approach is better suited for aperiodic structures, excited states, and broad spectral ranges, since it avoids the computational bottlenecks of sum-over-states approaches, as in the Fermi golden rule. This theoretical framework has been incorporated into efficient, user-friendly x-ray spectroscopy software which is now used routinely worldwide to simulate and analyze spectra. These theoretical tools provide an essential complement to synchrotron and next-generation light sources, which are used to investigate complex materials with ever increasing precision. Moreover, the synergism between theory, computation and experiment contributed by our research enhances scientific understanding and creates opportunities for innovations in materials and energy science and in many fields. As documented in this Report, this research grant has been remarkably successful in achieving these goals. In particular, this grant has supported the development of the x-ray spectroscopy software suite known as FEFF (named for an effective scattering amplitude f eff in the theory). The FEFF codes have become one of the premier tools for quantitative simulations of x-ray spectra as documented by many thousands of citations in the Web of Science and Google-Scholar.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Physics-informed neural networks for solving forward and inverse flow problems via the Boltzmann-BGK formulation

We report the Boltzmann equation with the Bhatnagar-Gross-Krook collision model (Boltzmann-BGK equation) has been employed to describe multiscale flows, i.e., from the hydrodynamic limit to free molecular flow. In this study we employ physics-informed neural networks (PINNs) to solve forward and inverse problems via the Boltzmann-BGK formulation (PINN-BGK), enabling PINNs to model flows in both the continuum and rarefied regimes. In particular, the PINN-BGK is composed of three sub-networks, i.e., the first for approximating the equilibrium distribution function, the second for approximating the non-equilibrium distribution function, and the third one for encoding the Boltzmann-BGK equation as well as the corresponding boundary/initial conditions. By minimizing the residuals of the governing equations and the mismatch between the predicted and provided boundary/initial conditions, we can approximate the Boltzmann-BGK equation for both continuous and rarefied flows. For forward problems, the PINN-BGK is utilized to solve various benchmark flows given boundary/initial conditions, e.g. Kovasznay flow, Taylor-Green flow, cavity flow, and micro Couette flow for Knudsen number up to 5. For inverse problems, we focus on rarefied flows in which accurate boundary conditions are difficult to obtain. We employ the PINN-BGK to infer the flow field in the entire computational domain given a limited number of interior scattered measurements on the velocity without using the (unknown) boundary conditions. Results for the two-dimensional micro Couette and micro cavity flows with Knudsen numbers ranging from 0.1 to 10 indicate that the PINN-BGK can infer the velocity field in the entire domain with good accuracy. Finally, we also present some results on using transfer learning to accelerate the training process. Specifically, we can obtain a three-fold speedup comparted to the standard training process (e.g., Adam plus L-BFG-B) for the two-dimensional flow problems considered in our work.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Shapes of rotating normal fluid He-3 versus superfluid He-4 droplets in molecular beams

Previous single-pulse extreme ultraviolet and X-ray coherent diffraction studies revealed that superfluid 4He droplets obtained in free jet expansion acquire sizable angular momentum, resulting in significant centrifugal distortion. Similar experiments with normal fluid 3He droplets may help elucidating the origin of the of the large degree of rotational excitation and highlight similarities and differences of dynamics in normal and superfluid droplets. Here, we present the first comparison of the shapes of isolated 3He and 4He droplets following expansion of the corresponding fluids in vacuum at temperatures as low as ~ 2 K. Large 3He and 4He droplets with average radii of ~160 nm and ~350 nm, respectively, were produced. We find that the majority of the 3He droplets in the beam correspond to rotating oblate spheroids with reduced average angular momentum ($\Lambda$) and reduced angular velocities ($\Omega$) similar to that of 4He droplets. Given the different physical nature of 3He and 4He, this similarity in $\Lambda$ and $\Omega$ may be surprising and suggest that similar mechanisms induce rotation regardless of the isotope. We hypothesized that the observed distribution of droplet sizes and angular momenta stem from processes in the dense region close to the nozzle. In this region, the significant velocity spread and collisions between the droplets induce excessive rotation followed by droplet fission. The process may repeat itself several times before the droplets enter the collision-fee high vacuum region further downstream.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Emergence of pseudoresonance in high-intensity resonant inelastic x-ray scattering

We report resonant inelastic x-ray scattering (RIXS) spectra of neon atoms interacting with intense x-ray pulses generated using an x-ray free-electron laser (XFEL). We find that an unexpected peak emerges near the 𝐾⁢𝛼 line of Ne, which does not coincide with any physical resonances of neon ions. We perform theoretical calculations based on a quantum-state-resolved rate-equation approach with x-ray-induced processes including possible resonant excitations. Our dynamics simulations demonstrate that a sequence of multiple resonant photoabsorption events are involved and the interplay of those multiple resonances in combination with the relatively large spectral bandwidth of XFEL radiation leads to the emergent resonance-like structure at a position where no resonances exist. Our finding offers critical guidance for future applications of high-intensity RIXS at XFEL facilities.

74 ATOMIC AND MOLECULAR PHYSICS↗