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DOE OSTI2021

Lorentzian dynamics and factorization beyond rationality

We investigate the emergence of topological defect lines in the conformal Regge limit of two-dimensional conformal field theory. We explain how a local operator can be factorized into a holomorphic and an anti-holomorphic defect operator connected through a topological defect line, and discuss implications on analyticity and Lorentzian dynamics including aspects of chaos. We derive a formula relating the infinite boost limit, which holographically encodes the “opacity” of bulk scattering, to the action of topological defect lines on local operators. Leveraging the unitary bound on the opacity and the positivity of fusion coefficients, we show that the spectral radii of a large class of topological defect lines are given by their loop expectation values. Factorization also gives a formula relating the local and defect operator algebras and fusion categorical data. We then review factorization in rational conformal field theory from a defect perspective, and examine irrational theories. On the orbifold branch of the c = 1 free boson theory, we find a unified description for the topological defect lines through which the twist fields are factorized; at irrational points, the twist fields factorize through “non-compact” topological defect lines which exhibit continuous defect operator spectra. Along the way, we initiate the development of a formalism to characterize non-compact topological defect lines.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2021

First-principles characterization of the magnetic properties of Cu 2 (OH) 3 Br

Low-dimensional spin-1/2 transition metal oxides and oxyhalides continue to be at the forefront of research investigating nonclassical phases such as quantum spin liquids. In this work, we examine the magnetic properties of the oxyhalide Cu 2 (OH) 3 Br in the botallackite structure using first-principles density functional theory, linear spin-wave theory, and exact diagonalization calculations. This quasi-two-dimensional system consists of Cu 2+ S = 1/2 moments arranged on a distorted triangular lattice. Our exact diagonalization calculations, which rely on a first-principles-based magnetic model, generate spectral functions consistent with inelastic neutron scattering data. By performing computational experiments to disentangle the chemical and steric effects of the halide ions, we find that the dominant effect of the halogen ions is steric in the Cu 2 (OH) 3 X series of compounds.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Pursuing Heteroleptic Ligand Design Principles for Photoactive Fe Complexes with Ultrafast X-ray Emission and Variable-Temperature Optical Spectroscopies

Understanding the key parameters that govern the photophysical and photochemical properties of transition metal complexes is essential for the development of efficient photosensitizers for photocatalytic applications. Achieving this objective necessitates clear and detailed investigations of their electronic excited states, for which time-resolved metal Kβ X-ray emission spectroscopy (XES) has proven highly effective. Here, we present a time-resolved Fe Kβ XES study of a heteroleptic Fe(II) polypyridyl carbene complex, [Fe(phen) 2 (C 4 H 10 N 4 )] 2+ (1; phen = 1,10-phenanthroline), utilizing both the valence-to-core and Kβ mainline spectral regions, complemented by variable-temperature transient optical absorption (VT-TA) spectroscopy. Detailed analysis of the time-resolved Kβ XES data, supported by density functional theory (DFT) calculations and an Eyring analysis of the VT-TA data, reveals parallel excited state relaxation dynamics that support an assignment of the long-lived excited state to a triplet metal-centered state. Placing these results in the context of prior studies of heteroleptic Fe(II) polypyridyl cyanide complexes motivated a series of DFT calculations to investigate the effects of ligand structural flexibility and arrangement. These calculations reinforce the experimentally derived conclusion that constraining structural flexibility with multidentate ligands significantly impacts the excited state relaxation dynamics. Furthermore, our study emphasizes that the arrangement of strong field ligands in heteroleptic complexes substantially affects the energy of Jahn–Teller active triplet metal-centered states in low-spin d 6 metal complexes. Together, these findings provide synthetic design principles for extending metal-to-ligand charge transfer excited state lifetimes of heteroleptic Fe complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Towards complete assignment of the infrared spectrum of the protonated water cluster H + (H 2 O) 21

The spectroscopic features of protonated water species in dilute acid solutions have been long sought after for understanding the microscopic behavior of the proton in water with gas-phase water clusters H + (H 2 O) n extensively studied as bottom-up model systems. We present a new protocol for the calculation of the infrared (IR) spectra of complex systems, which combines the fragment-based Coupled Cluster method and anharmonic vibrational quasi-degenerate perturbation theory, and demonstrate its accuracy towards the complete and accurate assignment of the IR spectrum of the H + (H 2 O) 21 cluster. The site-specific IR spectral signatures reveal two distinct structures for the internal and surface four-coordinated water molecules, which are ice-like and liquid-like, respectively. The effect of inter-molecular interaction between water molecules is addressed, and the vibrational resonance is found between the O-H stretching fundamental and the bending overtone of the nearest neighboring water molecule. The revelation of the spectral signature of the excess proton offers deeper insight into the nature of charge accommodation in the extended hydrogen-bonding network underpinning this aqueous cluster.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Probing atomic physics at ultrahigh pressure using laser-driven implosions

Abstract Spectroscopic measurements of dense plasmas at billions of atmospheres provide tests to our fundamental understanding of how matter behaves at extreme conditions. Developing reliable atomic physics models at these conditions, benchmarked by experimental data, is crucial to an improved understanding of radiation transport in both stars and inertial fusion targets. However, detailed spectroscopic measurements at these conditions are rare, and traditional collisional-radiative equilibrium models, based on isolated-atom calculations and ad hoc continuum lowering models, have proved questionable at and beyond solid density. Here we report time-integrated and time-resolved x-ray spectroscopy measurements at several billion atmospheres using laser-driven implosions of Cu-doped targets. We use the imploding shell and its hot core at stagnation to probe the spectral changes of Cu-doped witness layer. These measurements indicate the necessity and viability of modeling dense plasmas with self-consistent methods like density-functional theory, which impact the accuracy of radiation transport simulations used to describe stellar evolution and the design of inertial fusion targets.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2021

Orbital-resolved calculations of two-center interferences in linear triatomic molecules

In this report we perform ab initio calculations of high-harmonic spectroscopy (HHS) of two-center interference phenomena in oriented carbon-dichalcogen molecules, using time-dependent density functional theory (TDDFT). We show that by resolving the harmonic response into contributions from individual Kohn-Sham orbitals, we can extract target-specific characteristics for both the spectral amplitude and phase. We also discuss that this extraction is predicated on a careful analysis and normalization of the harmonic spectrum. Finally, we present field-free scattering calculations that mimic the recollision step in high-order-harmonic generation and allow the calculation of recombination dipole matrix elements without explicitly calculating the scattering states of a molecule. We show that the orbital-resolved TDDFT HHS results and results based on our field-free scattering calculations are in very good agreement with each other.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2024

Orbital-selective correlations and renormalized electronic structure in LiFeAs

Multiorbital physics is important to both the correlation physics and topological behavior of quantum materials. LiFeAs is a prototype iron pnictide suitable for in-depth investigation of this issue. Its electronic structure is strikingly different from the prediction of the noninteracting description. Here, a multiorbital Hubbard model is studied using a U(1) slave-spin theory. We demonstrate a mechanism for a substantial change to the Fermi surface, namely, orbital selectivity of the energy-level renormalization cooperating with its counterpart in quasiparticle spectral weight. Using this effect, we show how the dominating features of the electronic structure in LiFeAs are understood by the local correlations alone. In conclusion, our results set the stage to understand the origins and nature of both the unconventional superconductivity and likely electronic topology in this prototype iron pnictide and, more generally, reveal a remarkable degree of universality out of the seemingly complex multiorbital building blocks across a broad range of strongly correlated superconductors.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Towards megajoule x-ray lasers via relativistic four-photon cascade in plasma

Here, a theoretically highly efficient mechanism, operating at high laser intensities and powers, is identified for spectral transferring huge laser energies to shorter ultraviolet and x-ray wavelengths. With megajoule laser energies currently available at near-optical wavelengths, this transfer would, in theory, enable megajoule x-ray lasers, a huge advance over the millijoules x-ray pulses produced now. In fact, enabling even kilojoule x-ray lasers would still be a fantastic advance, and a more likely achievable one, considering practical experimental inefficiencies.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2024

Transducer Resolution Effect on Pressure Fluctuations Beneath Hypersonic Turbulent Boundary Layers

The size of a pressure transducer is known to affect the accuracy of measurements of wall-pressure fluctuations beneath a turbulent boundary layer because of spatial averaging over the sensing area of the transducer. In this paper, the effect of finite transducer size is investigated by applying spatial averaging or wavenumber filters to a database of hypersonic wall pressure generated from a direct numerical simulation (DNS) that simulates the turbulent portion of the boundary layer over a sharp 7° half-angle cone at nominally Mach 8. Here, a good comparison between the DNS and the experiment in the Sandia Hypersonic Wind Tunnel at Mach 8 is achieved after spatial averaging is applied to the DNS data over an area similar to the sensing area of the transducer. The study shows that a finite sensor size similar to that of the PCB132 transducer can cause significant attenuation in the root-mean-square and power spectral density (PSD) of wall-pressure fluctuations, and the attenuation effect is identical between cone and flat plate configurations at the same friction Reynolds number. The Corcos theory is found to successfully compensate for the attenuated high-frequency components of the wall-pressure PSD.

42 ENGINEERING↗

DOE OSTI2024

X-ray Spectral-Timing Pipeline to Investigate an Electron-Scattering Time Delay in Black Hole Accretion Disks [Slides]

The soft lag in black hole X-ray binaries (BHXRBs) refers to the time delay for the soft, thermal disk to respond to hard, variable coronal irradiation. This time lag increases from less than 1 ms to ~10 ms during the hard-to-soft state transition. Interpretations of soft lag trends appeal to changing the light-travel path via an evolving coronal height and/or inner accretion disk radius. Both interpretations neglect a time delay contribution from the reprocessing of irradiation inside the disk, where electron-scattering opacity dominates. A new theory considering a thermalization (electron scattering) time delay in the disk can plausibly produce ~10 ms time delays in the intermediate state. To further investigate the impacts of adding a time delay component from electron scattering in the disk, we are creating a spectral-timing pipeline that can analyze NICER (Neutron Star Interior Composition Explorer) X-ray observations of BHXRBs in outburst. In the near future, we will apply this spectral timing pipeline to develop a reverberation lag model from simulations that include the thermalization time delay from electron scattering in the disk.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2022

Role of Nematicity in Controlling Spin Fluctuations and Superconducting Tc in Bulk FeSe

FeSe undergoes a transition from a tetragonal to a slightly orthorhombic phase at 90 K and becomes a superconductor below 8 K. The orthorhombic phase is sometimes called a nematic phase because quantum oscillation, neutron, and other measurements detect a significant asymmetry in x and y. How nematicity affects superconductivity has recently become a matter of intense speculation. Here, we employ an advanced ab initio Green's function description of superconductivity and show that bulk tetragonal FeSe would, in principle, superconduct with almost the same critical temperature Tc as the nematic phase. The mechanism driving the observed nematicity is not yet understood. Since the present theory underestimates it, we simulate the full nematic asymmetry by artificially enhancing the orthorhombic distortion. For benchmarking, we compare theoretical spin susceptibilities against experimentally observed data over all energies and relevant momenta. When the orthorhombic distortion is adjusted to correlate with observed nematicity in spin susceptibility, the enhanced nematicity causes spectral weight redistribution in the Fe-3dxz and Fe-dyz orbitals, but it leads to at most a 10-15% increment in Tc. This is because the dxy orbital always remains the most strongly correlated and provides most of the source of the superconducting glue. Nematicity suppresses the density of states at the Fermi level; nevertheless, Tc increases, in contradiction to both BCS theory and the theory of Bose-Einstein condensation. We show how the increase is connected to the structure of the particle-particle vertex. Our results suggest that while nematicity may be an intrinsic property of bulk FeSe, it is not the primary force driving the superconducting pairing.

bulk FeSe↗

DOE OSTI2021

On duality of color and kinematics in (A)dS momentum space

We explore color-kinematic duality for tree-level AdS/CFT correlators in momentum space. We start by studying the bi-adjoint scalar in AdS at tree-level as an illustrative example. We follow this by investigating two forms of color-kinematic duality in Yang-Mills theory, the first for the integrated correlator in AdS 4 and the second for the integrand in general AdS d +1 . For the integrated correlator, we find color-kinematics does not yield additional relations among n -point, color-ordered correlators. To study color-kinematics for the AdS d +1 Yang-Mills integrand, we use a spectral representation of the bulk-to-bulk propagator so that AdS diagrams are similar in structure to their flat space counterparts. Finally, we study color KLT relations for the integrated correlator and double-copy relations for the AdS integrand. We find that double-copy in AdS naturally relates the bi-adjoint theory in AdS d +3 to Yang-Mills in AdS d +1 . We also find a double-copy relation at three-points between Yang-Mills in AdS d +1 and gravity in AdS d– 1 and comment on the higher-point generalization. By analytic continuation, these results on AdS/CFT correlators can be translated into statements about the wave function of the universe in de Sitter.

gauge-gravity correspondence↗

DOE OSTI2021

Cryogenic Vibrationally Resolved Photoelectron Spectroscopy of OH–(H2O): Confirmation of Multidimensional Franck-Condon Simulation Results for the Transition State of the OH + H2O Reaction

We present a transition state spectroscopic study of the OH + H2O reaction using the experimental technique of cryogenic Negative Ion Photoelectron Spectroscopy (NIPES). The recorded NIPE spectrum at 193 nm exhibits multiple vibrational progressions that include excitations to the shared H atom antisymmetric stretching mode with an interval of 0.32 eV as well as other progressions, mainly involving the H bending and O…O symmetric stretching modes. The Vertical Detachment Energy (VDE) was measured at 3.53 eV, whereas an upper limit for the Adiabatic Detachment Energy (ADE) was estimated at 2.90 eV. These values are in excellent agreement with the theoretically computed values of 3.51 eV and 2.83 eV respectively, obtained at the CCSD(T)/aug-cc-pV5Z level of theory. The recorded NIPE spectrum is in very good agreement when compared to the one recently reported from four-dimensional Franck-Condon simulations, in which a similar spectral profile was predicted. Besides observing the ground state, a charge-transfer excited state in the form of [OH–(H2O)+] is identified with a relative energy of 1.39 eV, well matching the previous prediction of 1.36 eV. This work was supported by U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, and performed using EMSL, a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory, which is operated by Battelle Memorial Institute for the DOE. The theoretical calculations were conducted on EMSL’s “Cascade” Supercomputer. This research also used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Cao, Wenjin↗

DOE OSTI2022

Comment on “Microhydration of Biomolecules: Revealing the Native Structures by Cold Ion IR Spectroscopy”

This paper presents a re-examination of the conclusions of a study reported in The Journal of Physical Chemistry Letters (Saparbaev et al., 2021, 12, 907) that compared the structure of microsolvated ions formed by electrospray ionization to those formed in the gas-phase via a previously published cryogenic ion trap approach. We conducted additional experiments that clearly show that most of the observed differences in the IR spectra can be accounted for by considering the different spectroscopic action schemes used to obtain them. In particular, the presence of the D 2 -tag induces shifts in some of the N-H and O-H peaks which need to be carefully considered before comparing spectra. Furthermore, once these spectral effects are taken into account, we show that both clustering approaches yields similar clusters structures for the small GlyH + (H 2 O)n species. Using unimolecular reaction rate theory, we also show that for the small complexes considered here, only the gas-phase equilibrium distribution of conformers should be expected in both experimental approaches. In addition, the barrier heights necessary to kinetically trap high-energy conformers at 298K is explored using a series of model polyalanine chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Replica symmetry breaking for the integrable two-site Sachdev–Ye–Kitaev model

We analyze a two-body non-Hermitian two-site Sachdev–Ye–Kitaev (SYK) model with the couplings of one site complex conjugated to the other site. This model, with no explicit coupling between the sites, shows an infinite number of second-order phase transitions, which is a consequence of the factorization of the partition function into a product over Matsubara frequencies. We calculate the quenched free energy in two different ways: first in terms of the single-particle energies and second by solving the Schwinger–Dyson equations of the two-site model. The first calculation can be done entirely in terms of a one-site model. The conjugate replica enters due to non-analyticities when Matsubara frequencies enter the spectral support of the coupling matrix. The second calculation is based on the replica trick of the two-site partition function. Both methods give the same result. The free-fermion partition function can also be rephrased as a matrix model for the coupling matrix. Up to minor details, this model is the random matrix model that describes the chiral phase transition of QCD, and the order parameter of the two-body model corresponds to the chiral condensate of QCD. Comparing to the corresponding four-body model, we are able to determine which features of the free energy are due to the chaotic nature of the four-body model. The high-temperature phase of both models is entropy dominated, and in both cases, the free energy is determined by the spectral density. The chaotic four-body SYK model has a low-temperature phase whose free energy is almost temperature-independent, signaling an effective gap of the theory even though the actual spectrum does not exhibit a gap. On the other hand, the low-temperature free energy of the two-body SYK model is not flat; in fact, it oscillates to arbitrarily low temperature. This indicates a less desirable feature that the entropy of the two-body model is not always positive in the low-temperature phase, which most likely is a consequence of the non-hermiticity.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2021

Switching of the electron-phonon interaction in 1 T –VSe 2 assisted by hot carriers

We apply an intense infrared laser pulse in order to perturb the electronic and vibrational states in the three-dimensional charge density wave material 1T-VSe 2 . Ultrafast snapshots of the light-induced hot carrier dynamics and nonequilibrium quasiparticle spectral function are collected using time- and angle-resolved photoemission spectroscopy. Furthermore, the hot carrier temperature and time-dependent electronic self-energy are extracted from the time-dependent spectral function, revealing that incoherent electron-phonon interactions heat the lattice above the charge density wave critical temperature on a timescale of (200 ± 40) fs. Density functional perturbation theory calculations establish that the presence of hot carriers alters the overall phonon dispersion and quenches efficient low-energy acoustic phonon scattering channels, which results in a new quasiequilibrium state that is experimentally observed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2023

Crucial role of thermal fluctuations and vertex corrections for the magnetic pseudogap

It is generally believed that in a two-dimensional metal, whose ground state is antiferromagnetically ordered with Q = (π,π), thermal (static) magnetic fluctuations give rise to precursor behavior above TN in which the spectral function of a hot fermion (the one for which k and k + Q are Fermi surface points) contains two peaks, separated by roughly the same energy as in the antiferromagnetically ordered state. The two peaks persist in some range of T > T N and eventually merge into a single peak at zero frequency. This behavior is obtained theoretically by departing from free fermions in a paramagnet and evaluating the dressed fermionic Green's function by summing up infinite series of diagrams with contributions from thermal magnetic fluctuations. We show, following that keeping vertex renormalization diagrams in these series is crucial as other terms only broaden the spectral function of a hot fermion but do not shift its maximum away from zero frequency. As the consequence, the magnetic pseudogap should be treated as an input for theories that neglect vertex corrections, such as, e.g., Eliashberg theory for magnetically mediated superconductivity. We also analyze the potential pseudogap behavior at T = 0. Here, we argue that it may exist, but only at a finite correlation length, and not as a precursor to antiferromagnetism.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2021

On the Stochastic Stability of Deep Markov Models

Deep Markov models (DMM) are generative models which are scalable and expressive generalization of Markov models for representation, learning, and inference problems. However, the fundamental stochastic stability guarantees of such models have not been thoroughly investigated. In this paper, we present a novel stability analysis method and provide sufficient conditions of DMM's stochastic stability. The proposed stability analysis is based on the contraction of probabilistic maps modeled by deep neural networks. We make connections between the spectral properties of neural network's weights and different types of used activation function on the stability and overall dynamic behavior of DMMs with Gaussian distributions. Based on the theory, we propose a few practical methods for designing constrained DMMs with guaranteed stability. We empirically substantiate our theoretical results via intuitive numerical experiments using the proposed stability constraints.

Drgona, Jan↗