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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Phenomenology of left-right symmetric dark matter

We present a detailed study of dark matter phenomenology in low-scale left-right symmetric models. Stability of new fermion or scalar multiplets is ensured by an accidental matter parity that survives the spontaneous symmetry breaking of the gauge group by scalar triplets. The relic abundance of these particles is set by gauge interactions and gives rise to dark matter candidates with masses above the electroweak scale. Dark matter annihilations are thus modified by the Sommerfeld effect, not only in the early Universe, but also today, for instance, in the Center of the Galaxy. Majorana candidates—triplet, quintuplet, bi-doublet, and bi-triplet—bring only one new parameter to the model, their mass, and are hence highly testable at colliders and through astrophysical observations. Scalar candidates—doublet and 7-plet, the latter being only stable at the renormalizable level—have additional scalar-scalar interactions that give rise to rich phenomenology. The particles under discussion share many features with the well-known candidates wino, Higgsino, inert doublet scalar, sneutrino, and Minimal Dark Matter. In particular, they all predict a large gamma-ray flux from dark matter annihilations, which can be searched for with Cherenkov telescopes. We furthermore discuss models with unequal left-right gauge couplings, g{sub R} ≠ g{sub L}, taking the recent experimental hints for a charged gauge boson with 2 TeV mass as a benchmark point. In this case, the dark matter mass is determined by the observed relic density.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

DISCOVERY OF RELATIVELY HYDROGEN-POOR GIANTS IN THE GALACTIC GLOBULAR CLUSTER ω CENTAURI

In this Letter, the results of our low-resolution spectroscopic survey for identifying hydrogen-deficient stars in the red giant sample of the globular cluster ω Cen are reported. Spectral analyses were carried out on the basis of the strengths of the (0, 0) MgH band and the Mg b triplet. In our sample, four giants were identified with weak/absent MgH bands in their observed spectra, which was unexpected for their well determined stellar parameters. The Mg abundances for the program stars were determined from the subordinate lines of the MgH band to the blue of the Mg b triplet, using the spectral synthesis technique. The derived Mg abundances for the program stars were as expected for the red giants of ω Cen, except for the four identified candidates. The determined Mg abundances of these four candidates are much lower than that expected for the red giants of ω Cen, and are unacceptable based on the strengths of the Mg b triplet in their observed spectra. Hence, a plausible explanation for the weak/absent MgH bands in the observed spectra of these stars is a relatively lower abundance of hydrogen in their atmospheres. These giants may belong to the group of helium-enriched red giants of ω Cen.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

Silicon vacancy-related centers in non-irradiated 6H-SiC nanostructure

We present the first findings of the silicon vacancy related centers identified in the non-irradiated 6H-SiC nanostructure using the electron spin resonance (ESR) and electrically-detected (ED) ESR technique. This planar 6H-SiC nanostructure represents the ultra-narrow p-type quantum well confined by the δ-barriers heavily doped with boron on the surface of the n-type 6H-SiC(0001) wafer. The new EDESR technique by measuring the only magnetoresistance of the 6H-SiC nanostructure under the high frequency generation from the δ-barriers appears to allow the identification of the isolated silicon vacancy centers as well as the triplet center with spin state S = 1. The same triplet center that is characterized by the large value of the zero-field splitting constant D and anisotropic g-factor is revealed by the ESR (X-band) method. The hyperfine (HF) lines in the ESR and EDESR spectra originating from the HF interaction with the {sup 14}N nucleus seem to attribute this triplet center to the N-V{sub Si} defect.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Final Progress Report

In this project we have established guidelines for the design on organic chromophores suitable for producing high triplet yields via singlet fission. We have proven their utility by identifying a chromophore of a structural class that had never been examined for singlet fission before, 1,3-diphenylisobenzofuran, and demonstrating in two independent ways that a thin layer of this material produces a triplet yield of 200% within experimental error. We have also designed a second chromophore of a very different type, again of a structural class that had not been examined for singlet fission before, and found that in a thin layer it produces a 70% triplet yield. Finally, we have enhanced the theoretical understanding of the quantum mechanical nature of the singlet fission process.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2015

Magnetic Field Enhancement of Organic Light‐Emitting Diodes Based on Electron Donor–Acceptor Exciplex

Reverse intersystem crossing (RISC) from triplet to singlet states has been recently introduced to photophysics of organic chromophores. One type of RISC occurs in donor (D)–acceptor (A) composites that form an exciplex manifold in which the energy difference, Δ E ST between the lowest singlet (S 1 ) and triplet (T 1 ) levels of the exciplex is small (<100 meV) thus allowing RISC at room temperature. This adds a delayed component to the photoluminescence emission that is widely known as thermally activated delayed fluorescence. Here, it is found that the electroluminescence in organic light‐emitting diodes (OLED) based on electron D–A exciplex is significantly enhanced (up to ≈40%) by applying magnetic field, due to the existence of an additional spin‐mixing channel between singlet and triplet states in the exciplex. The large magneto‐electroluminescence (MEL) in N , N , N ′, N ′‐tetrakis(4‐methoxyphenyl)benzidine: tris‐[3‐(3‐pyridyl)mesityl]borane [D–A] based OLEDs is demonstrated. These results are supported by magneto‐photoluminescence (MPL) measurements, and density functional theory calculations. Importantly, it is found that both MEL and MPL are thermally activated indicating the dominant role of the RISC process. The MEL( B ) response using the Δ g mechanism is analyzed, where the electron and hole g ‐values are different from each other because they reside in different molecules.

Basel, Tek↗
DOE OSTI2016

Intramolecular Singlet Fission in Oligoacene Heterodimers

In this Communication we investigate singlet fission (SF) in heterodimers comprising a pentacene unit covalently bonded to another acene as we systematically vary the singlet and triplet pair energies. We find that these energies control the SF process, where dimers undergo SF provided that the resulting triplet pair energy is similar or lower in energy than the singlet state. In these systems the singlet energy is determined by the lower energy chromophore, and the rate of SF is found to be relatively independent of the driving force. However, triplet pair recombination in these heterodimers follows the energy gap law. The ability to tune the energies of these materials provides a key strategy to study and design new SF materials – an important process for third generation photovoltaics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

The Acetylene Bridge in Intramolecular Singlet Fission: A Boon or A Nuisance?

Various analogues of the alkylsilylacetylene group are frequently used as auxiliary groups to enhance the solubility and stability of the acene dimer core, widely used as platforms to investigate intramolecular singlet fission (iSF) mechanisms. However, while in the 2,2’-linked dimers they are primarily auxiliary groups, these are essential fragments of the bridging units in 6,6’/5,5’-linked dimers, the two preferred choices for dimerization. The starkly different iSF dynamics observed in the two variants raise the question of what role the acetylene bridges play. Here, we systematically designed a set of (oligo-)para-phenylene bridged 2,2’-linked pentacene dimers with an additional acetylene fragment in the bridging unit to mimic the structure of 6,6’-linked dimers. Contrasting the results with previously reported analogous 2,2’-linked and 6,6’-linked pentacene dimers reveals that the acetylene bridges contribute to significant conformational freedom. This effect provides a mechanism to promote spin evolution within the triplet pair to achieve free triplets but also offers new parasitic pathways for triplet-pair recombination, revealing that this structural motif can be both a boon and a nuisance. Additionally, our analysis reveals that these bridges directly modify the electronic states, highlighting significant pitfalls of the standard chromophore-bridge-chromophore framework used to design and interpret photophysics of iSF materials.

14 SOLAR ENERGY↗
DOE OSTI2015

Spectroscopic and Computational Investigation of Low-Spin MnIII Bis(scorpionate) Complexes

Six-coordinate Mn III complexes are typically high-spin (S = 2), however, the scorpionate ligand, both in its traditional, hydridotris(pyrazolyl)borate form, Tp - and Tp* - (the latter with 3,5dimethylpyrazole substituents) and in an aryltris(carbene)borate (i.e. , N -heterocyclic carbene, NHC) form, [Ph(MeIm) 3 B] - , (MeIm = 3-methylimidazole) lead to formation of bis(scorpionate) complexes of Mn III with spin triplet ground states; three of which were investigated herein: [Tp 2 Mn]SbF 6 (1SBF 6 ), [Tp* 2 Mn]SbF 6 (2SBF 6 ), and [{Ph(MeIm) 3 B} 2 Mn]CF 3 SO 3 (3CF 3 SO 3 ). These trigonally symmetric complexes were studied experimentally by magnetic circular dichroism (MCD) spectroscopy (the propensity of 3 to oxidize to Mn IV precluded collection of useful MCD data) including variable temperatures and fields (VTVH-MCD) and computationally by ab initio CASSCF/NEVPT2 methods. These combined experimental and theoretical techniques establish the 3 A 2g electronic ground state for the three complexes, and provide information on the energy of the “conventional” high-spin excited state ( 5 E g ) and other, triplet excited states. These results show the electronic effect of pyrazole ring substituents in comparing 1 and 2. The tunability of the scorpionate ligand, even by perhaps the simplest change (from pyrazole in 1 to 3,5-dimethylpyrazole in 2) is quantitatively manifested through perturbations in ligand-field excited-state energies that impact ground-state zero-field splittings. The comparison with the NHC donor is much more dramatic. In 3, the stronger σ-donor properties of the NHC lead to a quantitatively different electronic structure, so that the lowest lying spin triplet excited state, 3 E g , is much closer in energy to the ground state than in 1 or 2. The zero-field splitting (zfs) parameters of the three complexes were calculated and in the case of 1 and 2 compare closely to experiment (lower by < 10%, < 2 cm -1 in absolute terms); for 3 the large magnitude zfs is reproduced, although there is ambiguity about its sign. The comprehensive picture obtained for these bis(scorpionate) Mn III complexes thus provides quantitative insight into the role played by the scorpionate ligand in stabilizing unusual electronic structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Electronic π-to-π* Excitations of Rhodamine Dyes Exhibit a Time-Dependent Kohn-Sham Theory “Cyanine Problem”

The longest-wavelength π-to-π* electronic excitations of rhodamine-like dyes (RDs) with different group16 heteroatoms (O, S, Se, Te) have been investigated. Time-dependent Kohn–Sham theory (TDKST) calculations were compared with coupled-cluster (CC) and equations-of-motion (EOM) CC results for π-to-π* singlet and triplet excitations. The RDs exhibit characteristics in the TDKST calculations that are very similar to previously investigated cyanine dyes, in the sense that the singlet energies obtained with nonhybrid functionals are too high compared with the CC results at the SD(T) level. The errors became increasingly larger for functionals with increasing amounts of exact exchange. TDKST with all tested functionals led to severe underestimations of the corresponding triplet excitations and overestimations of the singlet--triplet gaps. Long-range-corrected range-separated exchange and "optimal tuning" of the range separation parameter did not significantly improve the TDKST results. A detailed analysis suggests that the problem is differential electron correlation between the ground and excited states, which is not treated sufficiently by the relatively small integrals over the exchange-correlation response kernel that enters the excitation energy expression. As a result, numerical criteria are suggested that may help identify "cyanine-like" problems in TDKST calculations of excitation spectra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Compatibility of $\theta_{13}$ and the Type I Seesaw Model with $A_4$ Symmetry

We derive formulae for neutrino masses and mixing angles in a type I seesaw framework with an underlying A (4) flavor symmetry. In particular, the Majorana neutrino mass matrix includes contributions from an A (4) triplet, 1, 1('), and 1(") flavon fields. Using these formulae, we constrain the general A (4) parameter space using the updated global fits on neutrino mixing angles and mass squared differences, including results from the Daya Bay and RENO experiments, and we find predictive relations among the mixing parameters for certain choices of the triplet vacuum expectation value. In the normal hierarchy case, sizable deviation from maximal atmospheric mixing is predicted, and such deviation is strongly correlated with the value of θ(13) in the range of ~ (8 -10)°. On the other hand, such deviation is negligible and insensitive to θ(13) in the inverted mass hierarchy case. We also show expectations for the Dirac CP phase resulting from the parameter scan. Future refined measurements of neutrino mixing angles will test these predicted correlations and potentially show evidence for particular triplet vev patterns.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Combination of searches for heavy spin-1 resonances using 139 fb -1 of proton-proton collision data at $\sqrt{s}$ = 13 TeV with the ATLAS detector

A combination of searches for new heavy spin-1 resonances decaying into different pairings of W, Z, or Higgs bosons, as well as directly into leptons or quarks, is presented. The data sample used corresponds to 139 fb -1 of proton-proton collisions at $\sqrt{s}$ = 13 TeV collected during 2015–2018 with the ATLAS detector at the CERN Large Hadron Collider. Analyses selecting quark pairs (qq, bb, $t\overline{t}$, and tb) or third-generation leptons (τν and ττ) are included in this kind of combination for the first time. A simplified model predicting a spin-1 heavy vector-boson triplet is used. Cross-section limits are set at the 95% confidence level and are compared with predictions for the benchmark model. These limits are also expressed in terms of constraints on couplings of the heavy vector-boson triplet to quarks, leptons, and the Higgs boson. The complementarity of the various analyses increases the sensitivity to new physics, and the resulting constraints are stronger than those from any individual analysis considered. The data exclude a heavy vector-boson triplet with mass below 5.8 TeV in a weakly coupled scenario, below 4.4 TeV in a strongly coupled scenario, and up to 1.5 TeV in the case of production via vector-boson fusion.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Type II Seesaw leptogenesis

The Type II Seesaw Mechanism provides a minimal framework to explain the neutrino masses involving the introduction of a single triplet Higgs to the Standard Model. However, this simple extension was believed to be unable to successfully explain the observed baryon asymmetry of the universe through Leptogenesis. In our previous work (Phys. Rev. Lett. 128 (2022) 141801), we demonstrated that the triplet Higgs of the Type II Seesaw Mechanism alone can simultaneously generate the observed baryon asymmetry of the universe and the neutrino masses while playing a role in setting up Inflation. This is achievable with a triplet Higgs mass as low as 1 TeV, and predicts that the neutral component obtains a small vacuum expectation value $v_Δ$ < 10 keV. We find that our model has very rich phenomenology and can be tested by various terrestrial experiments as well as by astronomical observations. Particularly, we show that the successful parameter region may be probed at a future 100 TeV collider, upcoming lepton flavor violation experiments such as Mu3e, and neutrinoless double beta decay experiments. Additionally, the tensor-to-scalar ratio from the inflationary scenario will be probed by the LiteBIRD telescope, and observable isocurvature perturbations may be produced for some parameter choices. In this article, we present all the technical details of our calculations and further discussion of its phenomenological implications.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2018

A kernel machine method for detecting higher order interactions in multimodal datasets: Application to schizophrenia

Technological advances are enabling us to collect multimodal datasets at an increasing depth and resolution while with decreasing labors. Understanding complex interactions among multimodal datasets, however, is challenging. Here in this study, we tested the interaction effect of multimodal datasets using a novel method called the kernel machine for detecting higher order interactions among biologically relevant multimodal data. Using a semiparametric method on a reproducing kernel Hilbert space, we formulated the proposed method as a standard mixed-effects linear model and derived a score-based variance component statistic to test higher order interactions between multimodal datasets. The method was evaluated using extensive numerical simulation and real data from the Mind Clinical Imaging Consortium with both schizophrenia patients and healthy controls. Our method identified 13-triplets that included 6 gene-derived SNPs, 10 ROIs, and 6 gene-specific DNA methylations that are correlated with the changes in hippocampal volume, suggesting that these triplets may be important for explaining schizophrenia-related neurodegeneration. The performance of the proposed method is compared with the following methods: test based on only first and first few principal components followed by multiple regression, and full principal component analysis regression, and the sequence kernel association test. With strong evidence (p-value ≤0.000001), the triplet (MAGI2, CRBLCrus1.L, FBXO28) is a significant biomarker for schizophrenia patients. This novel method can be applicable to the study of other disease processes, where multimodal data analysis is a common task.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Development of (NO)Fe(N 2 S 2 ) as a Metallodithiolate Spin Probe Ligand: A Case Study Approach

The ubiquity of sulfur–metal connections in nature inspires the design of bi- and multimetallic systems in synthetic inorganic chemistry. Common motifs for biocatalysts developed in evolutionary biology include the placement of metals in close proximity with flexible sulfur bridges as well as the presence of π-acidic/delocalizing ligands. This Account will delve into the development of a (NO)Fe(N 2 S 2 ) metallodithiolate ligand that harnesses these principles. The Fe(NO) unit is the centroid of a N 2 S 2 donor field, which as a whole is capable of serving as a redox-active, bidentate S-donor ligand. Its paramagnetism as well as the ν(NO) vibrational monitor can be exploited in the development of new classes of heterobimetallic complexes. We offer four examples in which the unpaired electron on the {Fe(NO)} 7 unit is spin-paired with adjacent paramagnets in proximal and distal positions. First, the exceptional stability of the (NO)Fe(N 2 S 2 )-Fe(NO) 2 platform, which permits its isolation and structural characterization at three distinct redox levels, is linked to the charge delocalization occurring on both the Fe(NO) and the Fe(NO) 2 supports. This accommodates the formation of a rare nonheme {Fe(NO)} 8 triplet state, with a linear configuration. A subsequent FeNi complex, featuring redox-active ligands on both metals (NO on iron and dithiolene on nickel), displayed unexpected physical properties. Our research showed good reversibility in two redox processes, allowing isolation in reduced and oxidized forms. Various spectroscopic and crystallographic analyses confirmed these states, and Mössbauer data supported the redox change at the iron site upon reduction. Oxidation of the complex produced a dimeric dication, revealing an intriguing magnetic behavior. The monomer appears as a spin-coupled diradical between {Fe(NO)} 7 and the nickel dithiolene monoradical, while dimerization couples the latter radical units via a Ni 2 S 2 rhomb. Magnetic data (SQUID) on the dimer dication found a singlet ground state with a thermally accessible triplet state that is responsible for magnetism. A theoretical model built on an H 4 chain explains this unexpected ferromagnetic low-energy triplet state arising from the antiferromagnetic coupling of a four-radical molecular conglomerate. For comparison, two (NO)Fe(N 2 S 2 ) were connected through diamagnetic group 10 cations producing diradical trimetallic complexes. Antiferromagnetic coupling is observed between {Fe(NO)} 7 units, with exchange coupling constants (J) of -3, -23, and -124 cm –1 for Ni II , Pd II , and Pt II , respectively. This trend is explained by the enhanced covalency and polarizability of sulfur-dense metallodithiolate ligands. A central paramagnetic trans-Cr(NO)(MeCN) receiver unit core results in a cissoid structural topology, influenced by the stereoactivity of the lone pair(s) on the sulfur donors. This {Cr(NO)} 5 radical bridge, unlike all previous cases, finds the coupling between the distal Fe(NO) radicals to be ferromagnetic (J = 24 cm –1 ). The stability and predictability of this S = 1/2 moiety and the steric/electronic properties of the bridging thiolate sulfurs suggest it to be a likely candidate for the development of novel molecular (magnetic) compounds and possibly materials. The role of synthetic inorganic chemistry in designing synthons that permit connections of the (NO)Fe(N 2 S 2 ) metalloligand is highlighted as well as the properties of the heterobi- and polymetallic complexes derived therefrom.

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

Near-IR Luminescence Tuning in a Series of Chalcogenophene Carboxylate-Decorated Neodymium Dimers

Here, the solvothermal synthesis of a series of Nd dimers decorated with various chalcogenophene carboxylates and 2,2':6',2"-terpyridine of the general formula, [Nd 2 (µ-XC 5 H 3 O 2 ) 2 (XC 5 H 3 O 2 ) 4 (N 3 C 15 H 11 ) 2 (H 2 O) 2 ] where X = O, S, Se, and Te, is reported. The solid-state structures were characterized using single-crystal X-ray diffraction (scXRD) and all the complexes are isomorphous, despite substitution of the heterocyclic chalcogen; phase purity was confirmed via powder X-ray diffraction (pXRD). Vibrational spectroscopy was collected and correlations between chalcogen identity and the binding strength of the carboxylate groups of the chalcogenophene ligands with each metal center were shown to be independent of chalcogen identity. All four complexes displayed Nd(III)-based near-IR luminescence and exhibited ligand-sensitized emission. Varying the chalcogenophene chromophore enabled tuning of the sensitizing triplet state energy level, as evidenced by an 8-fold increase in the sensitization of the TeCA-decorated dimer relative to the other chalcogenophene congeners. This behavior was rationalized by comparing the Nd(III) acceptor and ligand donor states across the series. The donor triplet state of each ligand was estimated via low-temperature (77 K) phosphorescence measurements from 1:1 mixtures with Gd(III); these were found to be 24,631 cm –1 for furan-2-carboxylic acid (FCA), 23,764 cm –1 for thiophene-2-carboxylic acid (TCA), 22,548 cm –1 for selenophene-2-carboxylic acid (SeCA), and 21,186 cm –1 for tellurophene-2-carboxylic acid (TeCA). The greater sensitization efficiency of TeCA is the result of well-matched ligand donor and metal acceptor levels and thus suppression of nonradiative back-energy transfer. More broadly, triplet energy level information for these ligands serves as a guide for future application to other target metals based on the electronic properties necessary to effect efficient sensitization.

Coordination Chemistry↗
DOE OSTI2022

Long-Lived Photoluminescence of Molecular Group 14 Compounds through Thermally Activated Delayed Fluorescence

Photoluminescent molecules exploiting the sizable spin-orbit coupling constants of main group metals and metalloids to access long-lived triplet excited states are relatively rare compared to phosphorescent transition metal complexes. Here we report the synthesis of three air- and moisture-stable group 14 compounds E( Me PDP Ph ) 2 , where E = Si, Ge, or Sn and [ Me PDP Ph] 2- is the doubly deprotonated form of 2,6-bis(5- methyl-3-phenyl-1H-pyrrol-2-yl)pyridine. In solution, all three molecules exhibit exceptionally long-lived triplet excited states with lifetimes in the millisecond range and show highly efficient photoluminescence (Φ ≤ 0.49) due to competing prompt fluorescence and thermally activated delayed fluorescence at and around room temperature. Temperature-dependent steady-state emission spectra and photoluminescent lifetime measurements provided conclusive evidence for the two distinct emission pathways. Picosecond transient absorption spectroscopy allowed further analysis of the intersystem crossing (ISC) between singlet and triplet manifolds (τ ISC = 0.25-3.1 ns) and confirmed the expected trend of increased ISC rates for the heavier elements in otherwise isostructural compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗