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At least 73 records · Page 4

Hyperfine spectroscopy and laser cooling of the fermionic isotopes 47 Ti and 49 Ti

Here, we report on magneto-optical trapping of the two fermionic isotopes of atomic titanium, 47 Ti and 49 Ti . Unlike the even mass-number isotopes, which were recently laser cooled, 47 Ti and 49 Ti have nonzero nuclear spins and, consequently, their atomic levels are split by hyperfine structure. Combining and comparing theoretical calculations and atomic beam-spectroscopy measurements, we determine the hyperfine structures and isotope shifts of the 3⁢𝑑 2 ⁢4⁢𝑠 2 𝑎 3 ⁢𝐹 4 → 3⁢𝑑 2 ⁢( 3 𝑃)⁢4⁢𝑠⁢4⁢𝑝⁢( 3 𝑃 𝑜 ) 𝑦 5 ⁢𝐷$^o_4$ optical-pumping transition at optical wavelength 391 nm and the 3⁢𝑑 3 ⁢(4𝐹)⁢4⁢𝑠 𝑎 5 ⁢𝐹 5 → 3⁢𝑑 3 ⁢( 4 𝐹)⁢4⁢𝑝 𝑦 5 ⁢𝐺$^𝑜_6$ laser-cooling transition at wavelength 498 nm. With this information, we produce magneto-optical traps of both 47 Ti and 49 Ti by applying two additional tones of light to repump atoms to the maximum-spin states on the laser-cooling transition. Directly loading from the atomic flux of a titanium sublimation pump, we produce 47 Ti and 49 Ti traps with 731(190) and 1142(240) atoms, and with lifetimes of 330⁢(15) and 310⁢(8)⁢ ms, respectively.

atomic spectra↗

Smooth trends in fermium charge radii and the impact of shell effects

The quantum-mechanical nuclear-shell structure determines the stability and limits of the existence of the heaviest nuclides with large proton numbers Z ≳ 100. Shell effects also affect the sizes and shapes of atomic nuclei, as shown by laser spectroscopy studies in lighter nuclides. However, experimental information on the charge radii and the nuclear moments of the heavy actinide elements, which link the heaviest naturally abundant nuclides with artificially produced superheavy elements, is sparse. Here we present laser spectroscopy measurements along the fermium (Z = 100) isotopic chain and an extension of data in the nobelium isotopic chain (Z = 102) across a key region. Multiple production schemes and different advanced techniques were applied to determine the isotope shifts in atomic transitions, from which changes in the nuclear mean-square charge radii were extracted. A range of nuclear models based on energy density functionals reproduce well the observed smooth evolution of the nuclear size. Both the remarkable consistency of model prediction and the similarity of predictions for different isotopes suggest a transition to a regime in which shell effects have a diminished effect on the size compared with lighter nuclei.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Rapid spatial analysis of surrogate TRISO fuel particles using laser-induced breakdown spectroscopy image analysis

Laser-induced breakdown spectroscopy (LIBS) mapping enables rapid elemental and spatial analysis of solid samples. In this work, surrogate TRi-structural ISOtropic (TRISO) particles with various layers consisting of Zr, W, C, and Si were used to demonstrate the use of a new thickness measurement tool developed to analyze elemental images generated from LIBS maps. Zr particles with varying outer-layer thicknesses ranging from 16 to 32 μm were measured with scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) and LIBS with both a complementary metal-oxide-semiconductor (CMOS) detector and an intensified charged coupled device (ICCD) detector. LIBS maps of particles were completed using CMOS and ICCD spectrometers with effective spatial resolutions of 4 and 2 μm, respectively. The novel thickness measurement tool identified layer regions within a LIBS map and then identified the locations of the boundaries between these layers. The tool then generated up to 1000 random profiles stemming radially from the center region, which were used to measure the layer thickness/radius. This image analysis tool demonstrated LIBS's ability to provide values comparable with SEM-EDS (3.7% relative difference) along with a 95% reduction in measurement time. Furthermore, the precision of these measurements was on par with the SEM-EDS measurements at <15% relative standard deviation. Following the analysis of the Zr particles, W particles with increased complexity (e.g., five versus three layers) were analyzed using both the CMOS and ICCD spectrometers simultaneously. The spatial dimensions were extracted with an average relative difference of 2.7% and an average relative standard deviation of 9%.

Andrews, Hunter B. [Oak Ridge National Laboratory ↗

Using X-ray free-electron lasers for spectroscopy of molecular catalysts and metalloenzymes

The metal centers in metalloenzymes and molecular catalysts are responsible for the rearrangement of atoms and electrons during complex chemical reactions, and they enable selective pathways of charge and spin transfer, bond breaking/making and the formation of new molecules. Mapping the electronic structural changes at the metal sites during the reactions gives a unique mechanistic insight that has been difficult to obtain to date. The development of X-ray free-electron lasers (XFELs) enables powerful new probes of electronic structure dynamics to advance our understanding of metalloenzymes. The ultrashort, intense and tunable XFEL pulses enable X-ray spectroscopic studies of metalloenzymes, molecular catalysts and chemical reactions, under functional conditions and in real time. In this Technical Review, we describe the current state of the art of X-ray spectroscopy studies at XFELs and highlight some new techniques currently under development. With more XFEL facilities starting operation and more in the planning or construction phase, new capabilities are expected, including high repetition rate, better XFEL pulse control and advanced instrumentation. For the first time, it will be possible to make real-time molecular movies of metalloenzymes and catalysts in solution, while chemical reactions are taking place.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Search for 3D topological superconductors using laser-based spectroscopy (Final Technical Report)

The three-dimensional topological superconductor (3D TSC) is a novel quantum phase of matter that is predicted to exhibit exotic thermal and electrical properties, which may serve applications ranging from precision thermal management and sensing technologies to fault-tolerant quantum information processing. Over the past decade, there has been an intensive effort to realize 1D and 2D TSCs by artificially engineering them from combinations of already existing materials. For example, coupling conventional superconductors to spin-orbit coupled 1D nanowires or to 2D topological insulator surfaces by the proximity effect provides a route to realizing 1D and 2D TSCs respectively. However no artificial engineering strategy is available for a 3D TSC. Therefore, current searches are limited to intrinsically superconducting compounds whose topological properties are difficult to predict. The overarching goal of this project was to realize and to identify 3D TSCs in bulk single crystals using novel laser-based spectroscopic techniques. One major thrust was to develop ultralow temperature and ultra-high-resolution angle-resolved photoemission spectroscopy (ARPES) to directly measure the dispersion of Majorana excitations that are predicted to exist on the surfaces of 3D TSCs. Another major thrust was to develop a rational route to realize 3D TSCs by identifying their precursor phases. It is theoretically proposed that the critical fluctuations of certain ordered electronic phases can mediate Cooper pairing in odd-parity channels and lead to topological superconductivity. Therefore, 3D TSCs may potentially emerge upon suppressing these inversion symmetry broken precursor phases to a critical point with external perturbations such as pressure, strain or even light. To test this hypothesis, we studied candidate materials using a suite of symmetry-sensitive optical probes including rotational anisotropy optical second harmonic generation (RA-SHG) and time-resolved coherent phonon spectroscopy, all operable under high-pressure and low temperature environments.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Progress towards the FRIB-EDM 3 -Frontend: A tool to provide radioactive molecules from isotope harvesting for fundamental symmetry studies

The under-construction FRIB-EDM 3 -instrument was designed to study polar radioactive molecules (such as RaF) in transparent cryogenic solids by laser spectroscopy. The instrument is divided into a frontend- and a backend section. The frontend accepts an aqueous sample from isotope harvesting and provides a mass-separated molecular ion beam in an ultra-high vacuum environment. In the backend, the ions are guided into alkali-metal vapor and the resulting neutrals are co-deposited in a solid argon matrix to perform laser spectroscopy. Here, this work addresses the frontend of the instrument. The efficient ionization of harvested radioisotopes from aqueous samples is achieved with a spray-ionization method. Subsequently, the molecular ion beam is analyzed by mass-to-charge ratio by a quadrupole mass filter. To verify the feasibility of the approach, numerical simulations with the COMSOL and SIMION packages have been conducted. While the former was applied to study transport in ion funnels, the latter was used to investigate ion beam transmission through the lower pressure sections. Following promising simulation results, a first experimental setup is under construction.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Time-Resolved X-ray Emission Spectroscopy and Resonant Inelastic X-ray Scattering Spectroscopy of Laser Irradiated Carbon

The existence of liquid carbon as an intermediate phase preceding the formation of novel carbon materials has been a point of contention for several decades. Experimental observation of such a liquid state requires nonthermal melting of solid carbon materials at various laser fluences and pulse properties. Reflectivity experiments performed in the mid-1980s reached opposing conclusions regarding the metallic or insulating properties of the purported liquid state. Time-resolved X-ray absorption studies showed shortening of C–C bonds and increasing diffraction densities, thought to evidence a liquid or glassy carbon state, respectively. Nevertheless, none of these experiments provided information on the electronic structure of the proposed liquid state. Herein, we report the results of time-resolved resonant inelastic X-ray scattering (RIXS) and time-resolved X-ray emission spectroscopy (XES) studies on amorphous carbon (a-C) and ultrananocrystalline diamond (UNCD) as a function of delay time between the irradiating pulse and X-ray probe. For both a-C and UNCD, we attribute decreases in RIXS or XES signals to transition blocking, relaxation, and finally, ablation. Increased signal at 20 ps following the irradiation of the UNCD is attributed to the probable formation of nanoscale structures in the ablation plume. Further, differences in the amount of signal observed between a-C and UNCD are explained by the difference in sample thickness and, specifically, incomplete melting of the UNCD film. Comparisons to spectral simulations based on MD trajectories at extreme conditions indicate that the carbon state in our experiments is crystalline. Normal mode analysis confirmed that symmetrical bending or stretching of the C–C bonds in the diamond lattice results in XES spectra with small intensity differences. Overall, we observed no evidence of melting to a liquid state, as determined by the lack of changes in the spectral properties for up to 100 ps delays following the melting pulses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

From Coherence to Function: Exploring the Connection in Chemical Systems

The role of quantum mechanical coherences or coherent superposition states in excited state processes has received considerable attention in the last two decades largely due to advancements in ultrafast laser spectroscopy. These coherence effects hold promise for enhancing the efficiency and robustness of functionally relevant processes, even when confronted with energy disorder and environmental fluctuations. Understanding coherence deeply drives us to unravel mechanisms and dynamics controlled by order and synchronization at a quantum mechanical level, envisioning optical control of coherence to enhance functions or create new ones in molecular and material systems. In this frontier, the interplay between electronic and vibrational dynamics, specifically the influence of vibrations in directing electronic dynamics, has emerged as the leading principle. Here, two energetically disparate quantum degrees of freedom work in-sync to dictate the trajectory of an excited state reaction. Moreover, with the vibrational degree being directly related to the structural composition of molecular or material systems, new molecular designs could be inspired by tailoring certain structural elements. In the realm of chemical kinetics, our understanding of the dynamics of chemical transformations is underpinned by fundamental theories, such as transition state theory, activated rate theory, and Marcus theory. These theories elucidate reaction rates by considering the energy barriers that must be overcome for reactants to transform into products. Those barriers are surmounted by the stochastic nature of energy gap fluctuations within reacting systems, emphasizing that the reaction coordinate, the pathway from reactants to products, is not rigidly defined by a specific vibrational motion but encompasses a diverse array of molecular motions. While less is known about the involvement of specific intramolecular vibrational modes, their significance in certain cases cannot be overlooked. In this Account, we summarize key experimental findings that offer deeper insights into the complex electronic–vibrational trajectories encompassing excited states afforded from state-of-the-art ultrafast laser spectroscopy in three exemplary processes: photoinduced electron transfer, singlet–triplet intersystem crossing, and intramolecular vibrational energy flow in molecular systems. We delve into the rapid decoherence, or loss of phase and amplitude correlations, of vibrational coherences along promoter vibrations during subpicosecond intersystem crossing dynamics in a series of binuclear platinum complexes. This rapid decoherence illustrates the vibration-driven reactive pathways from the Franck–Condon state to the curve crossing region. We also explore the generation of new vibrational coherences induced by impulsive reaction dynamics rather than by the laser pulse in these systems, which sheds light on specific energy dissipation pathways and thereby on the progression of the reaction trajectory in the vicinity of the curve crossing on the product side. Another property of vibrational coherences, amplitude, reveals how energy can flow from one vibration to another in the electronic excited state of a terpyridine–molybdenum complex hosting a nonreactive dinitrogen substrate. In conclusion, a slight change in vibrational energy triggers a quasi-resonant interaction, leading to constructive wavepacket interference and ultimately intramolecular vibrational redistribution from a Franck–Condon active terpyridine vibration to a dinitrogen stretching vibration, energizing the dinitrogen bond.

Electrical energy↗

Exploring the Neutron Substructure with Advanced Polarized Helium-3 Targets (Or: How I Learned to Stop Worrying and Love Spectroscopy)

As we seek to understand the smallest, physical aspects of our universe, we cannot simply rely on our senses to probe the world around us as we did in the past. The smallest physical elements of our universe behave in strange, probabilistic ways and are completely invisible to the naked eye/ear/etc. So, we design clever experiments (such as scattering experiments) to probe these minute realms. Then, just as with the larger, observable world, we devise models and equations to describe what we think is happening. Due to the nature of the physical universe at the quantum scale and with the aid of symmetries such as Lorentz invariance, we can write down equations that describe the scattering, but the expressions contain functions, which we call ?form factors? and ?structure functions?, that we cannot compute from first principles. We can, however, formulate models that make predictions for these functions. By comparing our predictions with the observed data, we can gain insight into the validity of our models and thus a better physical understanding of what is happening at these minuscule scales. Studying the constituents inside of the nucleus of an atom adds another layer of difficulty if we can?t remove those components from the nucleus. This is the case with the neutron. When not bound in the nucleus with protons and other neutrons, the neutron will decay into a proton after about 15 minutes. So, we?re forced to study the neutron while it is still bound in the nucleus of an atom such as helium-3 (3He). For the last 1,000 years (rounding up), our group has developed high quality, polarized 3He targets made of an aluminosilicate glass. These targets are made in order to perform experiments at Jefferson Lab (JLab), experiments which let us determine the form factors and structure functions of the neutron by scattering polarized electrons from polarized neutrons (or rather polarized 3He). The specific experiments reported on in this thesis push the bounds of our understanding of the internal structure of the neutron. Good science is often about pushing experimental techniques to a new level. Toward that goal we study our polarized 3He targets both to advance the technology and to choose the best ones for our experiments. We do this using a process called nuclear magnetic resonance (NMR) to gauge the maximum polarization of a target and how fast the polarization decays with time. While these tests primarily provide us information that make analysis of our experimental scattering data possible, they also let us determine whether or not a target-cell is useful or even, dare I say, of spectacular quality. Our latest targets utilize a novel convection design allowing 3He to be polarized and quickly moved in front of the electron-beam, making it possible to use larger targets with higher electron-beam currents than ever before. This means more electrons scatter and we get more data. And by studying our targets in detail prior to using them in our experiments, we have found techniques to take effects which could have been detrimental to target quality and turn them to our advantage! It?s a real case of making lemonade out of lemons. We also use laser spectroscopy to study the absorption lines of alkali-metals in the target (potassium and rubidium, specifically). We add these alkali-metals to our target to facilitate polarizing the 3He. We can use the measurement of these pressure broadened absorption lines to determine the 3He density inside of the target with great precision. Historically, we understood the width of these lines would be dependent on the temperature of the target. Specifically, if I raise the temperature, the width should get bigger. I found that was not the case, which was very confusing at first, though very exciting now that I realize the data are self-consistent and suggestive of unexpected behavior. This thesis details the development of high quality, glass, polarized 3He targets for the 2020 An 1 /dn 2 and 2023 Gn E experiments, which utilized the first 3He convection targets and broke records in target quality. This thesis also covers the initial development of metal windows for the next-generation of 3He target-cells. Finally, this thesis documents the temperature dependence of the width of potassium (K) and rubidium (Rb) absorption lines as measured with laser spectroscopy.

Jantzi, Christopher↗

Dynamic computational optical fringe mitigation in tunable laser absorption spectroscopy

In optical spectroscopic systems where unwanted optical scattering cannot be eliminated, Fabry-Pérot etalons cause unpredictable changes in the spectral background. Frequent system calibration is then required to maintain the desired measurement accuracy, which presents a major limitation to the spectrometer. We introduce a computational approach to mitigate the adverse effects of optical fringing without hardware modifications. Motivated by experimental observations of complicated fringe behaviors, we simplify the problem by decomposing the fringe background into component etalons that can be addressed according to their individual characteristics. The effectiveness of the proposed method is demonstrated on a silicon photonic methane sensor, where accurate measurements of methane concentration are obtained from spectral data strongly affected by optical fringes.

Teng, Chu C. (ORCID:0000000152744835)↗