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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Prominent radiative contributions from multiply-excited states in laser-produced tin plasma for nanolithography

Extreme ultraviolet (EUV) lithography is currently entering high-volume manufacturing to enable the continued miniaturization of semiconductor devices. The required EUV light, at 13.5 nm wavelength, is produced in a hot and dense laser-driven tin plasma. The atomic origins of this light are demonstrably poorly understood. Here we calculate detailed tin opacity spectra using the Los Alamos atomic physics suite ATOMIC and validate these calculations with experimental comparisons. Our key finding is that EUV light largely originates from transitions between multiply-excited states, and not from the singly-excited states decaying to the ground state as is the current paradigm. Moreover, we find that transitions between these multiply-excited states also contribute in the same narrow window around 13.5 nm as those originating from singly-excited states, and this striking property holds over a wide range of charge states. We thus reveal the doubly magic behavior of tin and the origins of the EUV light.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1982

The Orion Nebula - Large-scale distribution of far-infrared and submillimeter line emission

Attention is given to the results of a study of radiative cooling in the interstellar clouds of the Orion Nebula through the emission of far-IR and submillimeter radiation. That the gas is 'clumpy' in the ionized region of the nebula is indicated by the far-IR observations of doubly ionized oxygen. With respect to the edges of the ionized region, the excitation temperature for the 3P1 state is 228 K and the observed emission can be plausibly associated with either ionization or shock fronts at the interface between the ionized and neutral region. Consideration is also given to the possibility of an ionized carbon halo, the turbulent state of the molecular cloud, and the need for further laboratory and theoretical analyses.

Harwit, M.↗
DOE OSTI2020

γ-ray measurements in fast-neutron-induced reactions on 203 Tl

Fast-neutron-induced reactions can be used to characterize reaction mechanisms, investigate nuclear structure, and impose constraints on nuclear models. Because of the difficulty in predicting such effects, experimental data are important to constrain models. Thallium isotopes located close to the doubly magic Pb 208 nucleus are important for comparison with shell-model calculations. Study the population of excited states in Tl 203 and lighter isotopes in such reactions. Our methods are as follows. γ -ray cross sections were measured. The data were taken by using the Germanium Array for Neutron-Induced Excitations spectrometer. The pulsed neutron source of the Los Alamos Neutron Science Center's Weapons Neutron Research facility provided neutrons in the energy range from 1 to 300 MeV. The time-of-flight technique was used to determine the incident neutron energies. Cross sections for emission of several γ rays in 20 reaction channels were determined. Candidates for the intruder 9 / 2 - state in Tl 203 , from the odd proton in the h 9 / 2 orbital, and the first 5 + states in Tl 202 , 204 , from admixture of configurations, were identified. The excitation energy of the candidate 9 / 2 - , π h 9 / 2 state is in good agreement with the theoretical prediction from a semi-empirical weak-coupling model and its half-life is in the range of tens of nanoseconds. The feeding of a previously known isomer in Tl 202 exhibits similarities with the feeding of other isomers in this mass region.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Deformation and Collectivity in Doubly Magic 208 Pb

Lead-208 is the heaviest known doubly magic nucleus and its structure is therefore of special interest. Despite this magicity, which acts to provide a strong restorative force toward sphericity, it is known to exhibit both strong octupole correlations and some of the strongest quadrupole collectivity observed in doubly magic systems. In this Letter, we employ state-of-the-art experimental equipment to conclusively demonstrate, through four Coulomb-excitation measurements, the presence of a large, negative, spectroscopic quadrupole moment for both the vibrational octupole 3$^{−}_{1}$ and quadrupole 2$^{+}_{1}$ state, indicative of a preference for prolate deformation of the states. The observed quadrupole moment is discussed in the context of the expected splitting of the 3 − ⊗3 − two-phonon states, due to the coupling of the quadrupole and octupole motion. These results are compared with theoretical values from three different methods, which are unable to reproduce both the sign and magnitude of this deformation. Thus, in spite of its well-studied nature, 208 Pb remains a puzzle for our understanding of nuclear structure.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Internal Conversion between Bright (1 1 B $^+_u$) and Dark (21 A $^-_g$) States in s- trans -Butadiene and s- trans -Hexatriene

Internal conversion (IC) between the two lowest singlet excited states, 1 1 B$_u^+$ and 2 1 A$_g^–$, of s-trans-butadiene and s-trans-hexatriene is investigated using a series of single- and multi- reference wave function and density functional theory (DFT) methodologies. Three independent types of the equation-of-motion coupled-cluster (EOMCC) theory capable of providing an accurate and balanced description of one- as well as two-electron transitions, abbreviated as δ-CR-EOMCC(2,3), DIP-EOMCC(4h2p){N o }, and DEA-EOMCC(4p2h){N u } or DEA-EOMCC(3p1h,4p2h){N u }, consistently predict that the 1 1 B$_u^+$/2 1 A$_g^–$ crossing in both molecules occurs along the bond length alternation coordinate. However, the analogous 1 1 B$_u^+$ and 2 1 A$_g^–$ potentials obtained with some multireference approaches, such as CASSCF and MRCIS(D), as well as with the linear-response formulation of time-dependent DFT (TDDFT), do not cross. Hence, caution needs to be exercised when studying the low-lying singlet excited states of polyenes with conventional multiconfigurational methods and TDDFT. The multistate many-body perturbation theory methods, such as XMCQDPT 2 , do correctly reproduce the curve crossing. Among the simplest and least expensive computational methodologies, the DFT approaches that incorporate the contributions of doubly excited configurations, abbreviated as MRSF (mixed reference spin-flip) TDDFT and SSR( 4,4 ), accurately reproduce our best EOMCC results. This is highly promising for nonadiabatic molecular dynamics simulations in larger systems.

36 MATERIALS SCIENCE↗
NASA NTRS1986

Double photon excitation of high-Rydberg atoms as a long-lived submillimeter detector

A method and apparatus for detecting submillimeter or IR radiation is disclosed. A rare gas, such as xenon, is supplied at its ground state via a pressurized cylinder and an adjustable leak valve into a cryogenically cooled detection area. The ground state of xenon is double photon excited to a particularized level of the Rydberg series by a resonance lamp and a laser. The doubly excited gas is then further excited by the radiation to be measured. A field ionization and an ion measurement indicative of the radiation intensity is achieved.

Chutjian, A. N.↗
DOE OSTI2022

Multistep Coulomb excitation of Ni 64 : Shape coexistence and nature of low-spin excitations

Here, the structure of 64 Ni, the heaviest stable Ni isotope, has been investigated via high-statistics, multistep safe Coulomb excitation to search for shape coexistence, a phenomenon recently observed in neutron-rich 66 Ni and 70 Ni as well as in doubly magic, N = 40, 68 Ni. The study was motivated by recent, state-of-the-art Monte Carlo shell-model calculations (MCSM), where a Hamiltonian with effective interactions incorporating the monopole tensor force predicts the existence of shape coexistence, also in the lower-mass 62,64 Ni isotopes. A set of transition and static E2 matrix elements for both yrast and near-yrast structures was extracted from the differential Coulomb excitation cross sections. From comparisons between the new results and MCSM as well as other shell-model calculations, a clearer picture of the structure of 64 Ni emerges. Specifically, the low-spin states are shown to be dominated by proton and neutron excitations mainly within the fp shell, with minimal contribution from the g 9/2 shape-driving neutron orbital. The agreement between experimental data and MCSM results indicates a small oblate deformation for the $0$$^{+}_{2}$ level and a spherical shape for the $0$$^{+}_{3}$ state. In addition, the small upper limit determined for the B(E2) probability of a transition associated with the decay of the recently observed 3463-keV, $0$$^{+}_{4}$ state agrees with its proposed assignment to a prolate shape, herewith providing first evidence for triple shape coexistence in a stable Ni isotope.

59 ≤ A ≤ 89↗
DOE OSTI2025

The Singlet–Triplet Gap of Cyclobutadiene: The CIPSI-Driven CC( P ; Q ) Study

An accurate determination of singlet−triplet gaps in biradicals, including cyclobutadiene in the automerization barrier region where one has to balance the substantial nondynamical many-electron correlation effects characterizing the singlet ground state with the predominantly dynamical correlations of the lowest-energy triplet, remains a challenge for many quantum chemistry methods. High-level coupled-cluster (CC) approaches, such as the CC method with a full treatment of singly, doubly, and triply excited clusters (CCSDT), are often capable of providing reliable results, but routine application of such methods is hindered by their high computational costs. We have recently proposed a practical alternative to converging the CCSDT energetics at small fractions of the computational effort, even when electron correlations become stronger and connected triply excited clusters are larger and nonperturbative, by merging the CC(P;Q) moment expansions with the selected configuration interaction methodology abbreviated as CIPSI. We demonstrate that one can accurately approximate the highly accurate CCSDT potential surfaces characterizing the lowest singlet and triplet states of cyclobutadiene along the automerization coordinate and the gap between them using tiny fractions of triply excited cluster amplitudes identified with the help of relatively inexpensive CIPSI Hamiltonian diagonalizations.

Basis sets↗
DOE OSTI2024

Plasmon-Driven Ammonia Decomposition on Pd(111): Hole Transfer’s Role in Changing Rate-Limiting Steps

Here, ammonia (NH 3 ) has the potential to be a hydrogen carrier because it can be transported and stored with ease, but only if it also can be decomposed easily when needed. Understanding how to control the frequently rate-limiting N–H bond breaking and N–N bond forming on catalytic surfaces may help design efficient means for NH 3 decomposition. Yuan et al. recently demonstrated photocatalytically selective N–H bond breaking in NH 3 on plasmon-driven aluminum–palladium (Al–Pd) antenna–reactor heterostructures. Using embedded correlated wavefunction (ECW) theory, we predict that the rate-determining step (RDS) for NH 3 decomposition on Pd(111) via thermocatalysis (dissociating the first N–H bond, *NH 3 → *NH 2 + *H, in the ground state, where * means adsorbed) differs from that via photocatalysis (dissociating the second N–H bond, *NH 2 → *NH + *H, in the excited state). This result is consistent with the measured catalytic efficiency and selectivity of NH 3 -deuterium (D 2 ) exchange reactions (an indirect way to measure N–H bond breaking) on Al–Pd heterodimers. We also determine the origin of the observed selectivity of thermocatalysis and photocatalysis on Pd(111) toward doubly deuterated (NHD 2 ) and monodeuterated (NH 2 D) products, respectively, and explore viability of the full NH 3 decomposition path, also via ECW theory. Additionally, we predict that the associative desorption of *N as N 2 from Pd(111) is extremely difficult in thermocatalysis at least at low surface coverages; metal-to-adsorbate hole transfer in photocatalysis stabilizes the transition state for the first N–H bond dissociation, shifting the RDS to the second N–H bond breaking. Furthermore, the redistribution of electrons around *N upon excitation reduces the electron density in the Pd–N bonds, which may lower the barrier for N 2 associative desorption in photocatalysis. Thus, light-induced, plasmon-mediated, excited-state hole transfer may provide an efficient mechanism to accelerate NH 3 decomposition.

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

Role of the Character of the Excited State of Singly Reduced Rh 2 (II,II) Intermediates on Photocatalytic Activity

Singly reduced intermediates have recently been implicated as photoactive intermediates in a number of important reactions; however, their photophysical properties remain poorly understood. A series of dirhodium(II,II) complexes, cis-[Rh 2 (p-R-Form) 2 (bncn) 2 ] 2+ (bncn = benzo[c]cinnoline; p-R-Form = N,N′-di-p-R-phenylformamidinate), where R = −OCH 3 (1), −CH 3 (2), −H (3), −F (4), −Cl (5), and −CF 3 (6), and their respective radical anions were prepared and their excited state properties were investigated. Complex 3 acted as a singlemolecule photocatalyst for H 2 production with red light. Substitution on the formamidinate ligands in 1−6 affected the energy of the Rh 2 (δ*)/Form(π,nb) highest occupied molecular orbital (HOMO), consistent with the metal/ligand-to-ligand charge transfer ( 1 ML-LCT) absorption maxima and the 3 ML-LCT excited state lifetime, ranging from 1.6 ns in 1 to 54 ns in 6 in CH 3 CN. The highest turnover number for photocatalytic H 2 evolution was observed for 3, and the lowest values were for 1 and 6. The radical anion, [Rh 2 ] − , formed during photocatalysis, was shown to absorb a photon and undergo a second reduction. The lifetimes of the doublet excited states of [3] − and [6] − were 0.49 and 0.24 ns, respectively. Calculations showed that the lowest energy excited state in [3] − was 2 ML-LCT, whereas that in [6] − was a bncn − → Rh 2 (σ*) ligand-to-metal charge transfer ( 2 LMCT) state. The 2 LMCT state stabilized across the series from [1] − to [6] − , pointing at its role in modulating the photophysical properties. This work highlights the importance of the reductive quenching of [Rh 2 ] − and the generation of the doubly reduced species to effectively catalyze hydrogen evolution.

Absorption↗
DOE OSTI2025

Lifting Triplet Degeneracy Through Organic‐Cation Driven Structural Perturbation to Modulate Luminescence of Sb 3+ ‐Doped Double Perovskite

The spin-orbit coupling (SOC) and the Jahn-Teller effect (JTE) alter the orbital degeneracy in materials, leading to unique optical, electronic, and magnetic properties essential in spintronics, quantum computing, and light-emitting diodes (LEDs). Here, the study employs luminescent p-xylylenediammonium (PXA) instead of Cs+ in Cs2NaInCl6 to yield 2D Sb3+-doped (PXA)2NaInCl8 double perovskite and demonstrates a non-degenerate triplet state resulting from enhanced JTE in the strong SOC regime, featuring distinct emission centers. Consequently, a broadband emission from both PXA and [SbCl6]3− spans the entire spectrum (350–750 nm), representing a rare single-source multi-emissive 2D perovskite. With in-depth comparative structural, temperature-dependent photo-physical, and theoretical studies, it is elucidated that the synergistic effect of SOC and JTE on the Eg and T2g lattice modes modulate the electronic structure of [SbCl6]3− by splitting the doubly degenerate E levels of 3 T$^{*}_{1u}$ into non-degenerate states. The physical model, supported by theoretical studies, explains the energy level splitting required to realize two kinds of radiative minima in the relaxed excited state.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Cross-shell excitations in Ca 46 studied with fusion reactions induced by a reaccelerated rare isotope beam

Discovering unexplored high-spin states in neutron-rich nuclei can open up a new direction to study band structure and the associated shell structure in isospin-asymmetric many-body systems. However, experimental reach has so far been limited to neutron-deficient or stable nuclei which are preferentially produced in fusion reactions used in such studies. Here in this paper, we report the first γ-ray spectroscopy with fusion reactions using a reaccelerated rare-isotope beam of 45 K performed at the ReA3 facility of the National Superconducting Cyclotron Laboratory. Using particle and γ-ray coincidence techniques, three new higher-lying states around 6 MeV and five new γ-ray transitions were identified for 46 Ca, suggesting three independent band structures formed from different particle-hole configurations. The rotational-like band built on the 0$^+_2$ state is established up to the tentatively assigned 6$^+_2$ state. New results are compared to large-scale shell model calculations, confirming the validity of the effective interaction describing particle-hole excitations across the Z=20 and N=28 shell gaps in the vicinity of doubly-magic 48 Ca.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Emerging nuclear collectivity in 124-130 Te

The emergence of nuclear collectivity near doubly-magic 132Sn was explored along the stable, eveneven 124-130Te isotopes. Preliminary measurements of the B(E2; 41+ → 21+) transition strengths are reported from Coulomb excitation experiments primarily aimed at measuring the g factors of the 41+ states. Isotopically enriched Te targets were excited by 198-205 MeV 58Ni beams. A comparison of transition strengths obtained is made to large-scale shell-model calculations with successes and limitations discussed.

coombes, Ben↗
DOE OSTI2021

Auger electron angular distributions following excitation or ionization from the Xe 3d and F 1s levels in xenon difluoride

Linearly polarized synchrotron radiation has been used to record polarization dependent, non-resonant Auger electron spectra of XeF 2 , encompassing the bands due to the xenon M 45 N 1 N 45 , M 45 N 23 N 45 , M 45 N 45 N 45 and M 45 N 45 V and fluorine KVV transitions. Resonantly excited Auger spectra have been measured at photon energies coinciding with the Xe 3d 5/2 → σ* and the overlapped Xe 3d 3/2 /F 1s → σ* excitations in XeF 2 . The non-resonant and resonantly excited spectra have enabled the Auger electron angular distributions, as characterized by the β A parameter, to be determined for the M 45 N 45 N 45 transitions. In the photon energy range over which the Auger electron angular distributions were measured, theoretical results indicate that transitions into the εf continuum channel dominate the Xe 3d photoionization in XeF 2 . In this limit, the theoretical value of the atomic alignment parameter (A 20 ) characterizing the core ionized state becomes constant. This theoretical value has been used to obtain the Auger electron intrinsic anisotropy parameters (α 2 ) from the β A parameters extracted from our non-resonant Auger spectra. For a particular Auger transition, the electron kinetic energy measured in the resonantly excited spectrum is higher than that in the directly ionized spectrum, due to the screening provided by the electron promoted into the σ* orbital. The interpretation of the F KVV Auger band in XeF 2 has been discussed in relation to previously published one-site populations of the doubly charged ions (XeF 2 2+ ). Here, the experimental results show that the ionization energies of the doubly charged states predominantly populated in the decay of a vacancy in the F 1s orbital in XeF 2 tend to be higher than those populated in the decay of a vacancy in the Xe 4d level in XeF 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Origin of Large Effective Phonon Magnetic Moments in Monolayer MoS 2

Recent helicity-resolved magneto-Raman spectroscopy measurement demonstrates large effective phonon magnetic moments of ~2.5 μ B in monolayer MoS 2 , highlighting resonant excitation of bright excitons as a feasible route to activate Γ-point circularly polarized phonons in transition metal dichalcogenides. However, a microscopic picture of this intriguing phenomenon remains lacking. In this work, we show that an orbital transition between the split conduction bands (Δ 0 = 4 meV) of MoS 2 couples to the doubly degenerate E" phonon mode (Ω 0 = 33 meV), forming two hybridized states. Our phononic and electronic Raman scattering measurements capture these two states: (i) one with predominantly phonon contribution in the helicity-switched channels and (ii) one with primarily orbital contribution in the helicity-conserved channels. An orbital-phonon coupling model successfully reproduces the large effective magnetic moments of the circularly polarized phonons and explains their thermodynamic properties. Strikingly, the Raman mode from the orbital transition is superimposed on a strong quasi-elastic scattering background, indicating the presence of spin fluctuations. As a result, the electrons excited to the conduction bands through the exciton exhibit paramagnetic behavior although MoS 2 is generally considered as a nonmagnetic material. By depositing nanometer-thickness nickel thin films on monolayer MoS 2 , we tune the electronic structure so that the A exciton perfectly overlaps with the 633 nm laser. The optimization of resonance excitation leads to pronounced tunability of the orbital-phonon hybridized states. Our results generalize the orbital-phonon coupling model of effective phonon magnetic moments to material systems beyond the paramagnets and magnets.

2D transition metal dichalcogenide↗
DOE OSTI2024

In-beam spectroscopy reveals competing nuclear shapes in the rare isotope 62 Cr

In recent decades, rareisotope facilities have enabled the study of short-lived, neutron-rich nuclei. Their measured properties indicate that shell structure changes in the regime of unbalanced neutron-to-proton ratios compared to that of stable nuclei. In the so-called islands of inversion in the nuclear chart – around the neutron-rich nuclei 32 Mg, 42 Si and 64 Cr, for example – the textbook shell-model picture predicts the presence of spherical shapes due to the respective magic neutron numbers of 20, 28, and 40 of these nuclei. However, nuclei in these regions turn out to be deformed in their ground states. Another hallmark of these islands is shape coexistence, where a nucleus assumes different shapes with excitation energy. Furthermore, we present evidence for this phenomenon from the observation of an excited 0 + state in 62 Cr, two neutrons away from the heart of the island of inversion around neutron number N = 40. We use large-scale shell-model calculations to interpret the results and report extrapolations for the doubly-magic nucleus 60 Ca.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Negative Ion Formation in Complex Heavy Systems

The project’s primary objective is to gain a fundamental theoretical understanding of the near-threshold electron attachment mechanism in low energy electron elastic scattering from complex heavy systems through the calculation of integral and differential cross sections and extract reliable electron affinities (EAs). The complex angular momentum (CAM), also known as Regge-pole methodology wherein is fully embedded the crucial electron-electron correlations and the core polarization interaction, is used for the investigations. Regge trajectories allow us to probe electron attachment at the fundamental level near threshold, thereby uncovering new manifestations, including the mechanism of nanocatalysis, and determine reliable EAs. Low-energy electron elastic scattering total cross sections (TCSs) for the lanthanide and actinide atoms and the fullerene molecules are calculated. From the TCSs ground, metastable and excited states anionic binding energies (BEs) are extracted and compared with the available measured and/or calculated EAs. Significantly, our calculated ground state anionic BEs correspond to the theoretically challenging to calculate EAs and they are used to assess the reliability of existing EAs. Doubly charged negative ions of atoms and molecules are proposed as novel tunable catalysts and demonstrated in the oxidation of water into peroxide. Negatively charged fullerene molecules are used to catalyze water oxidation to peroxide and water synthesis from H 2 and O 2 as well. Violation of time-reversal and particle-hole symmetries in strongly correlated Fermi systems are reviewed with the collaboration involving the International Laboratory of Fermi Condensation.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Ground and excited state properties of ThB − and ThB: a theoretical study

In the present work, we studied a series of electronic and spin–orbit states of ThB − and ThB using high-level multireference and coupled-cluster theories. We report the potential energy curves (PECs), equilibrium electron configurations, spectroscopic constants, energetics, and spin–orbit coupling effects of 17 and 19 electronic states of ThB − and ThB, respectively. The ground state of ThB − is a single-reference 1 3 Π with a 1σ 2 2σ 2 3σ 1 1π 3 electron configuration. Detachment of an electron from the doubly occupied 1π orbital of ThB − (1 3 Π) produces the single-reference ground electronic state of ThB (1 4 Σ − ). The ground spin–orbit states of ThB − and of ThB are 1 3 Π + 0 and 1 4 Σ − 3/2 , respectively. The vertical electron detachment energy (VDE) of ThB − and the adiabatic electron attachment energy (AEA) of ThB at our largest CBS-C-CCSD(T)+δT(Q)+δSO (complete basis set effect, spin–orbit effect, and triple and perturbative quadruple electron correlation effect added coupled-cluster theory with single, double, and perturbative triple excitations) level are 1.473 eV and 1.459, respectively. The reaction of Th( 3 F) + B( 2 P o ) produces the ground state of ThB with a bond energy of 2.843 eV. Finally, we estimated a heat of formation, Δ H 0 f (298 K), of 891.01 kJ mol −1 for the ThB molecule. The high-level findings of this work are expected to aid and motivate future experimental spectroscopic investigations of ThB and ThB − species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗