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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Excited-State Charge Transfer in Push–Pull Platinum(II) π-Extended Porphyrins Fused with Pentacenequinone

Platinum(II) π-extended porphyrins fused with pentacenequinone and dihydropentacene have been successfully synthesized. These porphyrins were investigated using various techniques including absorption, steady-state, and time-resolved phosphorescence spectroscopy and differential pulse voltammetry. UV–vis absorption spectra of pentacenequinone-fused porphyrins (SW-Pt1 and SW-Pt2) showed unusually broad and nontypical absorption patterns. Phosphorescence spectra of SW-Pt1, SW-Pt2, and SW-Pt3 displayed similar emissions in the 704–706 nm region indicating electronic transitions of similar origin; however, the triplet lifetimes were found to be quenched in the case of both SW-Pt1 and SW-Pt2, suggesting the occurrence of excited-state events. Facile reductions were obtained for both the pentacene-quinone-fused monomer (SW-Pt2) and dimer (SW-Pt1) and were identified to be located at the pentacenequinone components. Here, the observed orbital segregations for SW-Pt2 and SW-Pt1 from DFT calculations supported the possibility of charge transfer in these push–pull systems. Interestingly, the established energy level diagram revealed that the charge transfer from the triplet excited Pt porphyrin is thermodynamically an uphill process. Systematic studies involving both femtosecond and nanosecond transient absorption techniques revealed that the singlet excited Pt porphyrins undergo an intermediate charge transfer state prior to populating the triplet state, providing a plausible explanation for phosphorescence quenching. The lifetime of the intermediate charge transfer states was found to be 25.9 and 5.68 ps, respectively, for SW-Pt1 and SW-Pt2.

Charge transfer↗
DOE OSTI2022

Multichannel photodissociation dynamics in CS 2 studied by ultrafast electron diffraction

In this study, the structural dynamics of photoexcited gas-phase carbon disulfide (CS 2 ) molecules are investigated using ultrafast electron diffraction. The dynamics were triggered by excitation of the optically bright 1 B 2 ( 1 Σ u + ) state by an ultraviolet femtosecond laser pulse centred at 200 nm. In accordance with previous studies, rapid vibrational motion facilitates a combination of internal conversion and intersystem crossing to lower-lying electronic states. Photodissociation via these electronic manifolds results in the production of CS fragments in the electronic ground state and dissociated singlet and triplet sulphur atoms. The structural dynamics are extracted from the experiment using a trajectory-fitting filtering approach, revealing the main characteristics of the singlet and triplet dissociation pathways. Finally, the effect of the time-resolution on the experimental signal is considered and an outlook to future experiments provided.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Room‐Temperature Phosphorescent Platinum(II) Alkynyls with Microsecond Lifetimes Bearing a Strong‐Field Pincer Ligand

Abstract The use of organometallic triplet emitters in organic light emitting diodes (OLEDs) is motivated by the premise of efficient intersystem crossing leading to unit internal quantum efficiencies. However, since most devices are based on solid‐state components, an inherent limitation to square‐planar platinum(II) phosphors is their tendency toward aggregation‐based quenching. Here, a new class of emissive, four‐coordinate Pt II species based on the bisimidazolyl carbazolide (BIMCA) ligand is introduced, which displays highly efficient, long‐lived solid‐state phosphorescence at room temperature. A set of four BIMCAPt phenyl acetylides were synthesized that emit in the green ( λ max =507–540 nm) with >60 % quantum yield and millisecond lifetimes. The structures of the resulting species reveal a non‐planar structure imposed by steric clashes between BIMCA and the iodo or alkynyl co‐ligand. Ground‐state and photophysical characterization are presented. Density functional theory calculations indicate that the BIMCA ligand dominates the frontier orbitals along with the first Franck–Condon singlet and triplet excited states.

Liska, Tadeas↗
DOE OSTI2024

Interplay of coulomb and exciton–phonon coupling controls singlet fission dynamics in two pentacene polymorphs

Pentacene is an important model organic semiconductor in both the singlet exciton fission (SF) and organic electronics communities. We have investigated the effect of changing crystal structure on the SF process, generating multiple triplet excitons from an initial singlet exciton, and subsequent triplet recombination. Unlike for similar organic semiconductors that have strong SF sensitive to polymorphism, we find almost no quantitative difference between the kinetics of triplet pair (TT) formation in the two dominant polymorphs of pentacene. Both pairwise dimer coupling and momentum-space crystal models predict much faster TT formation from the bright singlet excited state of the Bulk vs ThinFilm polymorph, contrasting with the experiment. GW and Bethe–Salpeter equation calculations, including exciton–phonon coupling, reveal that ultrafast phonon-driven transitions in the ThinFilm polymorph compensate the intrinsically slower purely Coulomb-mediated TT formation channel, rationalizing the similarity in observed rates. Taking into account the influence of subtle structural distinctions on both the direct and phonon-mediated SF pathways reveals a predictive capability to these methods, expected to be applicable to a wide variety of molecular crystals.

14 SOLAR ENERGY↗
DOE OSTI2024

Ultrafast photochemistry and electron-diffraction spectra in n → (3s) Rydberg excited cyclobutanone resolved at the multireference perturbative level

We study the ultrafast time evolution of cyclobutanone excited to the singlet n → Rydberg state through non-adiabatic surface-hopping simulationsperformed at extended multi-state complete active space second-order perturbation (XMS-CASPT2) level of theory. These dynamics predict relaxation to the ground-state with a timescale of 822 ± 45 fs with minimal involvement of the triplets. The major relaxation path to the ground-state involves a three-state degeneracy region and leads to a variety of fragmented photoproducts. We simulate the resulting time-resolved electron-diffraction spectra, which track the relaxation of the excited state and the formation of various photoproducts in the ground state.

Chemistry↗
DOE OSTI2023

Hofstadter states and re-entrant charge order in a semiconductor moiré lattice

The emergence of moiré materials with flat bands provides a platform to systematically investigate and precisely control correlated electronic phases. Here, we report local electronic compressibility measurements of a twisted WSe2/MoSe2 heterobilayer which reveal a rich phase diagram of interpenetrating Hofstadter states and electron solids. We show that this reflects the presence of both flat and dispersive moiré bands whose relative energies, and therefore occupations, are tuned by density and magnetic field. At low densities, competition between moiré bands leads to a transition from commensurate arrangements of singlets at doubly occupied sites to triplet configurations at high fields. Hofstadter states (i.e., Chern insulators) are generally favored at high densities as dispersive bands are populated, but are suppressed by an intervening region of reentrant charge-ordered states in which holes originating from multiple bands cooperatively crystallize. Our results reveal the key microscopic ingredients that favor distinct correlated ground states in semiconductor moiré systems, and they demonstrate an emergent lattice model system in which both interactions and band dispersion can be experimentally controlled.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Side-chain ionization enables ultrafast intramolecular singlet fission in the azaquinodimethane skeleton

Singlet fission (SF) could significantly alleviate thermalization losses of high-energy photons, thus holding great potential for improving the power conversion efficiency of solar cells. Conventional SF materials require an intricate control of molecular packing motifs in the solid state to achieve efficient multiexciton generation. Small molecule intramolecular singlet fission (iSF) materials have emerged as promising alternatives and show great potential for practical device applications. However, the scope of such iSF materials remains rather limited, necessitating innovative molecular design strategies. Herein, we present how a side-chain ionization strategy leads to an iSF chromophore based on the azaquinodimethane (AQM) ring system. Systematic theoretical and spectroscopic analyses reveal that the direct attachment of electron-withdrawing ionic groups to the conjugated AQM core renders the originally fluorescent AQM nonemissive, leading to ionic AQM (iAQM) derivatives capable of ultrafast iSF to populate triplet-like species. Further fine-tuning of the iAQM skeleton imparts subtle intermolecular interactions that are indispensable for the efficient separation of triplet pairs following iSF in the aggregated state. Our findings offer unprecedented insights into molecular design and triplet exciton dynamics, laying the foundation for the discovery of rare molecular iSF materials.

Wu, Zixiang↗
DOE OSTI2025

Noble dark matter: Surprising elusiveness of dark baryons

Dark matter could be a baryonic composite of stronglyc upled constituents transforming under SU⁡(2) 𝐿 . We classify the SU⁡(2) 𝐿 representations of baryons in a class of simple confining dark sectors and find that the lightest state can be a pure singlet or a singlet that mixes with other neutral components of SU⁡(2) 𝐿 representations, which strongly suppresses the dark matter candidate’s interactions with the Standard Model. We focus on models with a confining SU⁡(𝑁 𝑐 ) and heavy dark quarks constituting vectorlike 𝑁 𝑓 -plet of SU⁢(2) 𝐿 . For benchmark 𝑁 𝑐 and 𝑁 𝑓 , we calculate baryon mass spectra, incorporating electroweak gauge boson exchange in the nonrelativistic quark model, and demonstrate that above TeV mass scales, dark matter is dominantly a singlet state. The combination of this singlet nature with the recently discovered ℋ-parity results in an inert state analogous to noble gases, hence we coin the term noble dark matter. Our results can be understood in the nonrelativistic effective theory that treats the dark baryons as elementary states, where we find singlets accompanying triplets, 5-plets, or more exotic representations. This generalization of WIMP-like theories is more difficult to find or rule out than dark matter models that include only a single SU⁡(2) 𝐿 multiplet (such as a wino), motivating new searches in colliders and a reanalysis of direct and indirect detection prospects in astrophysical observations.

dark matter direct detection↗
DOE OSTI2020

Singlet Fission in a para -Azaquinodimethane-Based Quinoidal Conjugated Polymer

The exploitation of singlet fission (SF) in photovoltaic devices is restricted by the limited number of SF materials available and the conflicting requirement of intermolecular interactions to satisfy both efficient SF and subsequent triplet extraction. Intramolecular SF (iSF) represents an emerging alternative and may prove simpler to implement in devices. Here, on account of the excellent chemical structure tunability and solution processability, conjugated polymers have emerged as promising candidates for iSF materials despite being largely underexplored. It remains a significant challenge to develop SF-capable conjugated polymers and achieve efficient dissociation of the formed triplet pairs simultaneously. In this contribution, we present a new iSF material in a para-azaquinodimethane-based quinoidal conjugated polymer. Using transient optical techniques, we show that an ultrafast iSF process dominates the deactivation of the excited state in such polymer, featuring ultrafast population (<1 ps) and stepwise dissociation of triplet pairs. Notably, these multiexciton states could further diffuse apart to produce long-lived free triplets (tens of μs) in strongly coupled aggregates in solid thin film. Such findings not only introduce a new iSF-active conjugated polymer to the rare SF material family but also shed unique insight into interchain interaction-promoted triplet pair dissociation in aggregates of conjugated polymers, thus openning new avenues for developing next-generation SF-based photovoltaic materials.

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

Observation of Persistent Zero Modes and Superconducting Vortex Doublets in UTe 2

Superconducting vortices can reveal electron pairing details and nucleate topologically protected states. Yet, vortices of bulk spin-triplet superconductors have never been visualized at the atomic scale. Recently, UTe 2 has emerged as a prime spin-triplet superconductor, but its superconducting order parameter is elusive, and whether time-reversal symmetry (TRS) is broken remains unsettled. Here, in this work, we visualize vortices on the (011) surface of ultraclean UTe 2 single crystals (T c = 2.1 K) using scanning tunneling microscopy (STM). We introduce $\frac{d^{2}𝐼}{d𝑉^{2}}$ imaging as an effective technique for vortex visualization in superconductors with substantial residual zero-energy density of states (DOS), as in UTe 2 . Anisotropic single-flux-quantum vortices, with coherence lengths of ∼12 nm (4 nm) parallel (perpendicular) to the a -axis, form a triangular vortex lattice (VL) under a small out-of-plane magnetic field. The invariance of vortex structures and VL under changes of field polarity and cooling history strongly supports time-reversal invariant superconductivity under zero field. At vortex cores (VCs), nonsplit, spectrally sharp zero-bias conductance peaks (ZBPs) persist up 8 T that are consistent with symmetry-protected Majorana zero modes (MZMs) in a topological vortex line. Close examination of vortex structures reveals a mirror-asymmetric doublet─one with ZBPs and another with an enhanced apparent gap, possibly originating from a field-induced multicomponent order parameter.

UTe2↗
DOE OSTI2021

Photonic analog of Mollow triplet with on-chip photon-pair generation in dressed modes

Making analogy with atomic physics is a powerful tool for photonic technology, witnessed by the recent development in topological photonics and non-Hermitian photonics based on parity–time symmetry. The Mollow triplet is a prominent atomic effect with both fundamental and technological importance. Here we demonstrate the analog of the Mollow triplet with quantum photonic systems. Photonic entanglement is generated with spontaneous nonlinear processes in dressed photonic modes, which are introduced through coherent multimode coupling. We further demonstrate the possibility of the photonic system to realize different configurations of dressed states, leading to modification of the Mollow triplet. Our work would enable the investigation of complex atomic processes and the realization of unique quantum functionalities based on photonic systems.

Cui, Chaohan↗
DOE OSTI2024

Quasi-Two-Dimensional Antiferromagnetic Spin Fluctuations in the Spin-Triplet Superconductor Candidate CeRh 2 As 2

The tetragonal heavy-fermion superconductor CeRh 2 ⁢As 2 (T c = 0.3 K) exhibits an exceptionally high critical field of 14 T for B ∥ c. It undergoes a field-driven first-order phase transition between superconducting states, potentially transitioning from spin-singlet to spin-triplet superconductivity. To further understand these superconducting states and the role of magnetism, we probe spin fluctuations in CeRh 2 ⁢As 2 using neutron scattering. Here, we find dynamic (π, π) antiferromagnetic (AFM) spin correlations with an anisotropic quasi-two-dimensional correlation volume. Our data place an upper limit of 0.31 μ B on the staggered magnetization of corresponding Néel orders at T = 0.08 K. Density functional theory calculations, treating Ce 4⁢ƒ electrons as core states, show that the AFM wave vector connects significant areas of the Fermi surface. Our findings indicate that the dominant excitations in CeRh 2 ⁢As 2 for ℏω⁢ < 1.2 meV are magnetic and suggest that superconductivity in CeRh 2⁢ As 2 is mediated by AFM spin fluctuations associated with a proximate quantum critical point.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Experimental and quantum mechanical characterization of an oxygen-bridged plutonium(IV) dimer

We report the synthesis and characterization of K 4 {[PuCl 2 (NO 3 ) 3 ] 2 (μ 2 -O)}·H 2 O, which contains the first known μ 2 -oxo bridge between two Pu IV metal centers. Adding to its uniqueness is the Pu-(μ 2 -O) bond length of 2.04 Å, which is the shortest of other analogous compounds. The Pu-(μ 2 -O)-Pu bridge is characterized by the mixing of s -, d -, and p -orbitals from Pu with the p -orbitals of O; the 5 f -orbitals do not participate in bonding. Natural bond orbital analysis indicates that Pu and O interact through one 3c-2e σ Pu-O-Pu and two 3c-2e π Pu-O-Pu bonding orbitals and that the electron density is highly polarized on the μ 2 -O. Bond topology properties analysis indicates that the Pu-(μ 2 -O) bond shares both ionic and covalent character. Quantum mechanical calculations also show that the dimer has multiconfigurational ground states, where the nonet, septet, quintet, triplet, and singlet are close in energy. This work demonstrates the interplay between experimental and computational efforts that is required to understand the chemical bonding of Pu compounds.

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

Interplay between Mixed and Pure Exciton States Controls Singlet Fission in Rubrene Single Crystals

Singlet fission (SF) is a multielectron process in which one singlet exciton S converts into a pair of separated triplet excitons T. SF is widely studied as it may help overcome the Shockley−Queisser efficiency limit for semiconductor photovoltaic cells. To elucidate and control the SF mechanism, great attention has been given to the identification of intermediate states in SF materials, which often appear elusive due to the complexity and fast time scales of the SF process. Here, we apply 14 fs-1 ms transient absorption techniques to high-purity rubrene single crystals to disentangle the intrinsic fission dynamics from the effects of defects and grain boundaries and to identify reliably the fission intermediates. Our data demonstrates that above-gap excitation directly generates a hybrid vibronically assisted mixture of singlet state and triplet-pair multiexciton [S/TT], which rapidly (<100 fs) and coherently branches into pure singlet or triplet excitations. The relaxation of [S/TT] to S is followed by a relatively slow and temperature-activated (48 meV activation energy) incoherent fission process. The SF competing pathways and intermediates revealed here unify the observations and models presented in previous studies of SF in rubrene and offer alternative strategies for the development of SF-enhanced photovoltaic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Fluctuation-induced odd-frequency spin-triplet pairing in a disordered electron liquid

Here we consider a two-dimensional disordered conductor in the regime when the superconducting phase is destroyed by the magnetic field. We analyze a combination of fluctuations of different origin which results in an effective interaction amplitude suitable for a spontaneous s-wave odd-frequency pairing instability. We observe that the end point of the superconductivity is a quantum critical point separating the conventional superconducting phase from a state with the odd-frequency spin-triplet pairing instability. We speculate that this could shed light on a rather mysterious insulating state observed in strongly disordered superconducting films in a broad region of the magnetic fields.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Hydroxy-substituted electron deficient Pd porphyrin cofactors illuminate ultrafast proton transfer reactions

Coordinated electron and proton movement drive bioenergetic functions. Relative to electron transfer reactions, tracking proton transport over fast-to-ultrafast time scales is challenging. Optical resolution of proton transfer dynamics can take advantage of chromophoric photoacids that not only trigger proton migration upon photoexcitation, but produce distinct spectroscopic changes associated with protonation/deprotonation. Here, in this work, we report the design of a hydroxy-substituted electron deficient Pd porphyrin, PPd(C 6 F 5 ) 3 OH; upon photoexcitation, the acidity constant of this weak acid (pKa = 6.49) dramatically drops (pKa* = 0.97). Electronic excitation of PPd(C 6 F 5 ) 3 OH triggers an ultrafast proton transfer reaction (PPd(C 6 F 5 ) 3 OH +:B + hυ → 1[PPd(C 6 F 5 ) 3 OH]* +:B → 1 [PPd(C 6 F 5 ) 3 O]−* + HB + ; τ PT = 342 fs) to a H-bonded base (B) in solution. Both PPd(C 6 F 5 ) 3 OH and its conjugate anion PPd(C 6 F 5 ) 3 O − exhibit distinct vis-NIR spectral features for their respective ground and excited states. Because the electroni-cally excited triplet lifetimes of these species exceed tens of microseconds, the PPd(C 6 F 5 ) 3 OH photoacid defines an ideal cofactor to probe light-triggered proton release and track long-range proton migration in protein environments.

Palladium↗
DOE OSTI2025

The Electronic Structure of Zirconium and Hafnium Monochalcogenides

High-level ab initio CCSD(T) and spin–orbit icMRCI+Q calculations were used to predict potential energy curves (PECs) for the lowest-lying states of ZrO, ZrS, HfO, and HfS. The prediction of the ground state is basis set dependent at the icMRCI+Q level for ZrO and ZrS due to the small singlet–triplet splitting between the lowest 1 Σ + and 3 Δ states. CCSD(T) with a spin orbit correction predicted the 1 Σ + ground state in agreement with experiment. New all-electron basis sets were developed for Hf to improve the results over those predicted by use of effective core potentials (ECPs) that subsume the 4f electrons into the definition of the core. The use of the new DK-4f basis sets rather than ECPs became more important for HfO and HfS where there is a lack of a good core–valence separation. icMRCI+Q, CCSD(T), and DFT calculations for the spectroscopic parameters of ZrO, ZrS, HfO, and HfS were benchmarked with available experimental data. Bond dissociation energies (BDEs) of these four systems were calculated at the Feller–Peterson–Dixon (FPD) level to be 762.1 (ZrO), 543.5 (ZrS), 803.8 (HfO), and 575.1 kJ/mol (HfS), in excellent agreement with experiment. The HfS BDE was remeasured using the R3PI method, providing an updated experimental measurement of D 0 (HfS) = 5.978 ± 0.002 eV = 576.8 ± 0.2 kJ/mol. This experimental value, combined with experimental measurements of the ionization energies of Hf and HfS, gives the cationic BDE of D 0 (Hf + -S) = 5.124 ± 0.002 eV = 494.4 ± 0.2 kJ/mol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Photochemical Upconversion in Water Using Cu(I) MLCT Excited States: Role of Energy Shuttling at the Micellar/Water Interface

Photochemical upconversion (UC) through triplet–triplet annihilation (TTA), which employs a visible absorbing triplet photosensitizer and an annihilator, is a process that generates a high energy photon from two lower energy photons. TTA-UC has been largely developed in pure organic solvents and solid-state polymeric constructs while featuring near exclusive use of rare and expensive metals within the photosensitizer. In this current investigation, we demonstrate that TTA-UC from the long lifetime earth-abundant photosensitizer [Cu(dsbtmp) 2 ](PF) 6 (dsbtmp = 2,9-di(sec-butyl)-3,4,7,8-tetramethyl-1,10-phenanthroline), abbreviated as Cu-PS, functions in water through encapsulation within a cationic-based assembly. Cetyltrimethylammonium bromide was the surfactant of choice as it electrostatically binds the negatively charged water-soluble 10-phenylanthracene-9-carboxylate (PAC) acceptor/annihilator and ultimately facilitates energy transfer across the interface. Efficient triplet–triplet energy transfer (TTET) from Cu-PS to the PAC acceptor was achieved in this aqueous assembly. Unfortunately, the hindered mobility of the PAC moieties ultimately hampered the annihilation process, and this was reflected in attenuated TTA rates and efficiencies. The combined experimental data illustrated that the water-soluble PAC acceptor was able to vectorially deliver the excited-state energy stored in Cu-PS across the interface into the bulk aqueous solution by engaging in excited-state electron transfer with methyl viologen acceptors. Lastly, these results are important for remotely operating photoredox reactions in water while rendering a photosensitizer spatially isolated in the hydrophobic core of a micelle.

36 MATERIALS SCIENCE↗