Ultrafast Resonant Interatomic Coulombic Decay Induced by Quantum Fluid Dynamics
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72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
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One-dimensional air temperature measurements by air resonance enhanced multiphoton Ionization thermometry (ART)
In this work, a detailed calibration study is performed to establish non-intrusive one-dimensional (1D) rovibrational temperature measurements in unseeded air, based on air resonance enhanced multiphoton ionization thermometry (ART). ART is generated by REMPI (resonance enhanced multi-photon ionization) of molecular oxygen and subsequent avalanche ionization of molecular nitrogen in a single laser pulse. ART signal, the fluorescence from the first negative band of molecular nitrogen, is directly proportional to the 2-photon transition of molecular oxygen C 3 Π (v = 2) ← X 3 Σ (v’=0), which is used to determine temperature. Experimentally, hyperfine structures of the O 2 rotational branches with high temperature sensitivity are selectively excited through a frequency-doubled dye laser. Electron-avalanche ionization of N 2 results in the fluorescence emissions from the first negative bands of N 2 + near 390, 425, and 430nm, which are captured as a 1D line by a gated intensified camera. Post processing of the N 2 + fluorescence yields a 1D thermometry line that is representative of the air temperature. It is demonstrated that the technique provides ART fluorescence of ∼5cm in length in the unseeded air, presenting an attractive thermometry solution for high-speed wind tunnels and other ground test facilities.
42 ENGINEERING↗
Two-photon double photoionization of atomic Mg by ultrashort pulses: Variation of angular distributions with pulse length
We investigate the two-photon double ionization of atomic magnesium induced by ultrashort pulses. Though the initial and final state symmetries are comparable to the same process in helium, in stark contrast the range of photon energies for which nonsequential ionization is the only open pathway is narrow (less than 1 eV) in magnesium. Thus several sequential ionization pathways feature heavily in these processes. Nonetheless, it is found that for pulse durations between 0.25 and 2.0 fentoseconds, the joint angular dependence of the ejected electrons can depend sensitively on pulse length, varying between the strictly back-to-back ejection characteristic of nonsequential ionization to other distributions. The significance of excited-state correlating configurations in representing the initial state of magnesium is discussed in the light of their consequences for the resulting angular distributions at photon energies where sequential ionization can access intermediate states that lie nearby in energy, particularly for longer pulses.
74 ATOMIC AND MOLECULAR PHYSICS↗
Interactions between atmospheric pressure plasmas and metallic catalyst particles in packed bed reactors
Atmospheric-pressure plasmas sustained in packed bed reactors (PBRs) are being investigated for chemical conversion of gases and pollution control. Metallic catalysts added to the surfaces of the dielectric beads of PBRs can increase the energy efficiency and selectivity of chemical processes by reducing operating temperature and providing additional reaction pathways. In this paper, results from a computational investigation of plasma surface interactions between micron-scale metallic catalysts and humid-air plasmas in PBRs are discussed. Here we found that high plasma density regions form in the proximity of the metallic catalysts. These higher-density plasma regions were confirmed experimentally using ICCD imaging. The intense plasmas result from geometrical electric field enhancement and redistribution of charges within the conductive particles, leading to further enhancement. The high electric field at the triple points of the catalysts can produce electric field emission of electrons, which provides a pre-ionization source or additional source of electrons. These regions of high electric field and sources of electrons guide discharges towards the catalysts and increases fluxes of excited species, ions, electrons and photons to their surfaces. These fluxes are focused primarily at the triple points between the metal, dielectric and gas. As a result, the catalyst is locally heated, which could lead to further increased rates of thermocatalytic reactions on the surface. Surface roughness of the metal inclusions can lead to additional electric field enhancement, which changes the character of the discharges in the vicinity of the catalysts while reducing breakdown voltage.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Probing C60 Fullerenes from within Using Free Electron Lasers
Fullerenes, such as C60, are ideal systems to investigate energy redistribution following substantial excitation. Ultra-short and ultra-intense free electron lasers (FELs) have allowed molecular research in a new photon energy regime. FELs have allowed the study of the response of fullerenes to X-rays, which includes femtosecond multi-photon processes, as well as time-resolved ionization and fragmentation dynamics. This perspective: (1) provides a general introduction relevant to C60 research using photon sources, (2) reports on two specific X-ray FEL-based photoionization investigations of C60, at two different FEL fluences, one static and one time-resolved, and (3) offers a brief analysis and recommendations for future research.
Berrah, Nora (ORCID:0000000332311164)↗
Competing ionization and dissociation: Extension of the energy-dependent frame transformation to the gerade symmetry of H 2
This article solves two major tasks that frequently arise in the theory of electron collisions with a target molecular cation. First, it extends the energy-dependent frame transformation (EDFT) treatment, which is needed to map fixed-nuclei electron-molecule scattering matrices into an energy-dependent laboratory-frame scattering matrix with vibrational channel indices. The EDFT mapping can now be carried out even when the target molecule possesses multiple low-energy potential curves, significantly transcending previous applications. Second, it implements a method to extract the rest of the full laboratory-frame scattering matrix, i.e., the columns and rows describing input and/or output dissociation channels. The treatment is benchmarked in this article against the essentially exact solution of a refined two-dimensional model of the singlet gerade Σ symmetry of H 2 . Our tests demonstrate that the theory accurately maps fixed-nuclei scattering information, of the type provided by existing electron-molecule computer codes, into a laboratory-frame scattering matrix that includes both ionization and dissociation. Furthermore, this treatment can provide a general framework applicable to a broad class of electron collision processes involving diatomic target ions, suitable for an accurate description of challenging processes such as dissociative recombination.
74 ATOMIC AND MOLECULAR PHYSICS↗
Time-resolved momentum imaging of UV photodynamics in structural isomers of iodopropane probed by site-selective XUV ionization
The photodynamics of 1- and 2-iodopropane (1 and 2-IP) were studied in a time-resolved scheme incorporating ultraviolet (UV) excitation and extreme ultraviolet (XUV) probing, which initiates photoionization selectively from the I 4d core orbital. UV absorption in the A-band of both isomers leads to prompt C–I bond fission, with significant disposal of internal energy into the propyl radical product. Site-selective ionization enables a range of charge transfer (CT) processes between the nascent highly charged iodine ions and neutral propyl radicals, dependent on the interfragment distance at the instant of ionization. Subtle differences in the dynamics of these CT processes between the two isomers are observed. In 1-IP, the kinetic energies of iodine ions produced by UV photodissociation and subsequent XUV multiple ionization increased notably over the first few hundred femtoseconds, which could be understood in terms of differing gradients along the photodissociation coordinates of the neutral and polycationic states involved in the pump and probe steps, respectively. Led by a recent report of HI elimination in UV photoexcited 2-IP [Todt et al., Phys. Chem. Chem. Phys., 22(46), 27338 (2020)], we also model the most likely signatures of this process in the present experiment, and can identify signal in the 2-IP data (that is absent or significantly weaker in the data from the unbranched 1-IP isomer) that is consistent with such a process occurring on ultrafast timescales.
Allum, Felix [Deutsches Elektronen-Synchrotron (DE↗
Ultrafast time-resolved x-ray absorption spectroscopy of ionized urea and its dimer through ab initio nonadiabatic dynamics
Investigating the early dynamics of chemical systems following ionization is essential for our understanding of radiation damage. However, experimental as well as theoretical investigations are very challenging due to the complex nature of these processes. Time-resolved x-ray absorption spectroscopy on a femtosecond timescale, in combination with appropriate simulations, is able to provide crucial insights into the ultrafast processes that occur upon ionization due to its element-specific probing nature. In this theoretical study, we investigate the ultrafast dynamics of valence-ionized states of urea and its dimer employing Tully's fewest switches surface hopping approach using Koopmans' theorem to describe the ionized system. We demonstrate that following valence ionization through a pump pulse, the time-resolved x-ray absorption spectra at the carbon, nitrogen, and oxygen K-edges reveal rich insights into the dynamics. Excited states of the ionized system give rise to time-delayed blueshifts in the x-ray absorption spectra as a result of electronic relaxation dynamics through nonadiabatic transitions. Moreover, our statistical analysis reveals specific structural dynamics in the molecule that induce time-dependent changes in the spectra. For the urea monomer, we elucidate the possibility to trace effects of specific molecular vibrations in the time-resolved x-ray absorption spectra. For the urea dimer, where ionization triggers a proton transfer reaction, we show how the x-ray absorption spectra can reveal specific details on the progress of proton transfer.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Fundamental data for modeling electron-induced processes in plasma remediation of perfluoroalkyl substances
Plasma treatment of per- and polyfluoroalkyl substances (PFAS) contaminated water is a potentially energy efficient remediation method. In this treatment, an atmospheric pressure plasma interacts with surface-resident PFAS molecules. Developing a reaction mechanism and modeling of plasma–PFAS interactions requires fundamental data for electron–molecule reactions. In this paper, we present results of electron scattering calculations, potential energy landscapes and their implications for plasma modelling of a dielectric barrier discharge in PFAS contaminated gases, a first step towards modelling of plasma–water–PFAS intereactions. It is found that the plasma degradation of PFAS is dominated by dissociative electron attachment with the importance of other contributing processes varying depending on the molecule. All molecules posses a large number of shape resonances – transient negative ion states – from near-threshold up to ionization threshold. These states lie in the region of the most probable electron energies in the plasma (4–5 eV) and consequently are expected to further enhance the fragmentation dynamics in both dissociative attachment and dissociative excitation.
54 ENVIRONMENTAL SCIENCES↗
DOE Plasma Science Center - Predictive Control of Plasma Kinetics: Multi-Phase and Bounded Systems (Final Report DE-SC0001939)
Low temperature plasmas (LTPs) are the plasmas of electron-volt (eV) physics and eV technologies. LTPs have characteristic electron temperatures of a few eV and fractional ionizations that are typically small. Since LTPs have electron temperatures commensurate with the threshold energies of excited states in neutral atoms and molecules, power transfer from electrons to these atoms and molecules efficiently produces activated species (e.g., radicals, excited states, photons). Acceleration of ions in the sheaths of LTPs to energies of tens to hundreds of eV enable activation of surface modifying processes – sputtering, etching, deposition. With such properties, LTPs are often and beneficially used in technological devices, ranging from etching and deposition in microelectronics and solar cell fabrication, to hardening of surgical instruments. LTPs harbor fundamental science issues that are intellectually challenging and rewarding. At the same time, there are enormous societal benefits that are enabled by LTPs. The entire present-day and future information technology infrastructure owes its very existence to LTPs. Renewable energy sources, such as solar cell arrays, could not be economically produced in the absence of deposition and etching by LTPs. In acknowledgment of the importance of LTPs, the DOE Office of Fusion Energy Sciences supported the Plasma Science Center for Predictive Control of Plasma Kinetics: Multi-Phase and Bounded Systems from August 2009 to July 2021, consisting of an initial 5-year grant, 3 funded extensions and 2 no-cost extensions. This is the final report of the Center in which the productivity of the Center is discussed in terms of publications, impact and personnel. High-lights of the research performed in the Center are provided.
36 MATERIALS SCIENCE↗
Lectures on statistical mechanics
Presented here is a transcription of the lecture notes from Professor Allan N. Kaufman’s graduate statistical mechanics course Physics 212A and 212B at the University of California Berkeley from the 1972–1973 academic year. 212A addressed equilibrium statistical mechanics with topics: fundamentals (micro-canonical and sub-canonical ensembles, adiabatic law and action conservation, fluctuations, pressure, and virial theorem), classical fluids and other systems (equation of state, deviations from ideality, virial coefficients and van der Waals potential, canonical ensemble and partition function, quasistatic evolution, grand-canonical ensemble and partition function, chemical potential, simple model of a phase transition, quantum virial expansion, numerical simulation of equations of state, and phase transition), chemical equilibrium (systems with multiple species and chemical reactions, law of mass action, Saha equation, chemical equilibrium including ionization and excited states), and long-range interactions (including Coulomb, dipole, and gravitational interactions, Debye–Hückel theory, and shielding). 212B addressed nonequilibrium statistical mechanics with topics: fundamentals (definitions: realizations, moments, characteristic function, and discrete variables), Brownian motion (Langevin equation, fluctuation–dissipation theorem, spatial diffusion, Boltzmann’s H-theorem), Liouville and Klimontovich equations, Landau equation (derivation, elaboration, and H-theorem, and irreversibility), Markov processes and Fokker–Planck equation (derivations of the Fokker–Planck equation and a master equation), linear response and transport theory (linear Boltzmann equation, linear response theory of Kubo and Mori, relation of entropy production to electrical conductivity, transport relations and coefficients, normal mode solutions of the transport equations, sketch of a generalized Langevin equation method for transport theory), and an introduction to nonequilibrium quantum statistical mechanics.
plasma dynamics↗
Distinguishing the XUV-induced Coulomb explosion dynamics of iodobenzene using covariance analysis
The primary and secondary fragmentation dynamics of iodobenzene following its ionization at 120 eV were determined using three-dimensional velocity map imaging and covariance analysis. Site-selective iodine 4d ionization was used to populate a range of excited polycationic parent states, which primarily broke apart at the carbon-iodine bond to produce I+ with phenyl or phenyl-like cations (C n H x + or C n H, with n = 1 – 6 and x = 1 – 5). The molecular products were produced with varying degrees of internal excitation and dehydrogenation, leading to stable and unstable outcomes. This further allowed the secondary dynamics of C 6 H x 2+ intermediates to be distinguished using native-frame covariance analysis, which isolated these processes in their own centre-of-mass reference frames. Furthermore, the mass resolution of the imaging mass spectrometer used for these measurements enabled the primary and secondary reaction channels to be specified at the level of individual hydrogen atoms, demonstrating the ability of covariance analysis to comprehensively measure the competing fragmentation channels of aryl cations, including those involving intermediate steps.
74 ATOMIC AND MOLECULAR PHYSICS↗
Ultrafast Molecular Frame Quantum Tomography
Here, we develop and experimentally demonstrate a methodology for a full molecular frame quantum tomography (MFQT) of dynamical polyatomic systems. We exemplify this approach through the complete characterization of an electronically nonadiabatic wave packet in ammonia (NH 3 ). The method exploits both energy and time-domain spectroscopic data, and yields the lab frame density matrix (LFDM) for the system, the elements of which are populations and coherences. The LFDM fully characterizes electronic and nuclear dynamics in the molecular frame, yielding the time- and orientation-angle dependent expectation values of any relevant operator. For example, the time-dependent molecular frame electronic probability density may be constructed, yielding information on electronic dynamics in the molecular frame. In NH 3 , we observe that electronic coherences are induced by nuclear dynamics which nonadiabatically drive electronic motions (charge migration) in the molecular frame. Here, the nuclear dynamics are rotational and it is nonadiabatic Coriolis coupling which drives the coherences. Interestingly, the nuclear-driven electronic coherence is preserved over longer timescales. In general, MFQT can help quantify entanglement between electronic and nuclear degrees of freedom, and provide new routes to the study of ultrafast molecular dynamics, charge migration, quantum information processing, and optimal control schemes.
74 ATOMIC AND MOLECULAR PHYSICS↗
Analytic Gradients for Equation-of-Motion Coupled Cluster with Single, Double, and Perturbative Triple Excitations
Understanding the process of molecular photoexcitation is crucial in various fields, including drug development, materials science, photovoltaics, and more. The electronic vertical excitation energy is a critical property, for example in determining the singlet-triplet gap of chromophores. However, a full understanding of excited-state processes requires additional explorations of the excited-state potential energy surface and electronic properties, which is greatly aided by the availability of analytic energy gradients. Owing to its robust high accuracy over a wide range of chemical problems, equation-of-motion coupled-cluster with single and double excitations (EOM-CCSD) is a powerful method for predicting excited state properties, and the implementation of analytic gradients of many EOM-CCSD (excitation energies, ionization potentials, electron attachment energies, etc.) along with numerous successful applications high- lights the flexibility of the method. In specific cases where a higher level of accuracy is needed or in more complex electronic structures, the inclusion of triple excitations becomes essential, for example, in the EOM-CCSD* approach of Saeh and Stanton. In this work, we derive and implement for the first time the analytic gradients of EOMEE-CCSD*, which also provides a template for analytic gradients of related ex- cited state methods with perturbative triple excitations. Here, the capabilities of analytic EOMEE-CCSD* gradients are illustrated by several representative examples.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ionization of Free and Confined Atoms and Ions (Final Technical Report)
Over the almost 22-year duration of this theoretical research project, a great deal of progress has been made in the understanding of the ionization of free and confined atomic and molecular systems along with a recent particular emphasis upon studies of the ultrafast time-delay phenomenon in the photoemission process. Our methods have emphasized the role of many-body interactions and relativistic effects in the various processes we have studied. The advances that we have made over the course of this project have been in the areas nondipole effects in the photoionization process, inner-shell photoemission from negative atomic ions, excited state photoionization of neutral atoms and positive atomic ions, Cooper minima in quadrupole photoionization, relativistic interaction in the photoionization of atoms and negative atomic ions, photoionization of the fullerene molecule C 60 along with the photoionization of atomic and molecular systems confined in the C 60 molecule, confinement resonances in endohedral atom photoemission, interchannel coupling effects in photoionization, Wigner time delay in free and confined atoms and ions, angular effects in Wigner time delay in atomic photoionization, photoionization of superheavy atoms and the influence of core relaxation on the photoionization of atomic systems, among others. In the course of this project, we have had extensive collaboration with experimentalists where we have explained the physics of numerous measurements and pointed the way to new laboratory investigations with our calculations. We have also collaborated with a number of theorists as well. Thus, owing to these many collaborations with scientists not funded by DOE, we have leveraged the DOE support rather considerably. To illustrate the depth and breadth of the theoretical investigations, listed below are the 138 refereed and invited publications that cite DOE support. These publications detail the many contributions made over the period of this project.
74 ATOMIC AND MOLECULAR PHYSICS↗
Radiolytically reworked Archean organic matter in a habitable deep ancient high-temperature brine
Abstract Investigations of abiotic and biotic contributions to dissolved organic carbon (DOC) are required to constrain microbial habitability in continental subsurface fluids. Here we investigate a large (101–283 mg C/L) DOC pool in an ancient (>1Ga), high temperature (45–55 °C), low biomass (10 2 −10 4 cells/mL), and deep (3.2 km) brine from an uranium-enriched South African gold mine. Excitation-emission matrices (EEMs), negative electrospray ionization (–ESI) 21 tesla Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), and amino acid analyses suggest the brine DOC is primarily radiolytically oxidized kerogen-rich shales or reefs, methane and ethane, with trace amounts of C 3 –C 6 hydrocarbons and organic sulfides. δ 2 H and δ 13 C of C 1 –C 3 hydrocarbons are consistent with abiotic origins. These findings suggest water-rock processes control redox and C cycling, helping support a meagre, slow biosphere over geologic time. A radiolytic-driven, habitable brine may signal similar settings are good targets in the search for life beyond Earth.
Science & Technology - Other Topics↗
Strong-field ionization of the triplet ground state of O 2
Using strong-field ionization as a probe, we observe highly nonperiodic evolution of the spin-rotation wave packet launched by a nonionizing femtosecond pulse in oxygen. The nonperiodicity is readily apparent only in rotationally cold molecules that are pumped with a weak alignment pulse. We show that this behavior is a consequence of the spin-rotation and the spin-spin couplings in the triplet ground state of the neutral molecule. A model that includes these couplings in the field-free Hamiltonian but in neither the alignment nor the ionization step explains most of the observed dynamics, suggesting that neither process depends explicitly on the electronic spin. We also show that the angle dependence of strong-field ionization can be retrieved from the delay-dependent signal even when coupling to spin complicates the rotational dynamics.
74 ATOMIC AND MOLECULAR PHYSICS↗
Low-dose high-resolution $\mathrm{TOF}$-$\mathrm{PET}$ using ionization-activated multi-state low-$\mathrm{Z}$ detector media
We propose PET scanners using low atomic number media that undergo a persistent local change of state along the paths of the Compton recoil electrons. Measurement of the individual scattering locations and angles, deposited energies, and recoil electron directions allows using the kinematical constraints of the 2-body Compton scattering process to perform a statistical time-ordering of the scatterings, with a high probability of precisely identifying where the gamma first interacted in the detector. In these cases the Line-of-Response is measured with high resolution, determined by the underlying physics processes and not the detector segmentation. There are multiple such media that act through different mechanisms. As an example in which the change of state is quantum-mechanical through a change in molecular configuration, rather than thermodynamic, as in a bubble chamber, we present simulations of a two-state photoswitchable organic dye, a ‘Switchillator’, that is activated to a fluorescent-capable state by the ionization of the recoil electrons. The activated state is persistent, and can be optically excited multiple times to image individual activated molecules. Energy resolution is provided by counting the activated molecules. Location along the LOR is implemented by large-area time-of-flight MCP-PMT photodetectors with single photon time resolution in the tens of ps and sub-mm spatial resolution. Simulations indicate a large reduction of dose.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗