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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

GPU-Accelerated Solution of the Bethe–Salpeter Equation for Large and Heterogeneous Systems

We present a massively parallel GPU-accelerated implementation of the Bethe–Salpeter equation (BSE) for the calculation of the vertical excitation energies (VEEs) and optical absorption spectra of condensed and molecular systems, starting from single-particle eigenvalues and eigenvectors obtained with density functional theory. The algorithms adopted here circumvent the slowly converging sums over empty and occupied states and the inversion of large dielectric matrices through a density matrix perturbation theory approach and a low-rank decomposition of the screened Coulomb interaction, respectively. Further computational savings are achieved by exploiting the nearsightedness of the density matrix of semiconductors and insulators to reduce the number of screened Coulomb integrals. We scale our calculations to thousands of GPUs with a hierarchical loop and data distribution strategy. The efficacy of our method is demonstrated by computing the VEEs of several spin defects in wide-band-gap materials, showing that supercells with up to 1000 atoms are necessary to obtain converged results. We discuss the validity of the common approximation that solves the BSE with truncated sums over empty and occupied states. In conclusion, we then apply our GW-BSE implementation to a diamond lattice with 1727 atoms to study the symmetry breaking of triplet states caused by the interaction of a point defect with an extended line defect.

Absorption spectra↗
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 OSTI2025

Charge Transfer and Recombination Pathways through Fullerene Guests in Porphyrin-Based MOFs

Porphyrin-based metal–organic frameworks (MOFs) offer a unique platform for building porous donor–acceptor networks that exhibit long-lived charge separation and transport upon incorporation of electron acceptor guest species. Here, in this work, porphyrin-based MOFs, PCN-222(H 2 ) and PCN-222(Zn), synthesized as nanoparticle suspensions, are successfully infiltrated with fullerene acceptor molecules, C 60 or PC 61 BM, in both polar and nonpolar solvent environments. The location and relative binding strength of these guest species are evaluated through a combination of N 2 physisorption measurements, photoluminescence quenching, and UV–vis absorption titration experiments. Semiempirical tight binding calculations are used to screen potential locations of the fullerene guest within the MOF pores, and hybrid density functional theory (DFT)-computed interaction energies confirm the energetically favorable positions. The fundamental photophysics of these donor–acceptor host–guest combinations are probed using ultrafast transient absorption spectroscopy. Sub-picosecond electron transfer involving initial exciplex population is observed, with slow charge recombination lifetimes on the order of τ ~1 ns for all systems in both dimethylformamide and 1,4-dioxane. Charge recombination occurs through population of fullerene and/or framework porphyrin triplet states depending on the porphyrin metalation status. The photophysics of the fullerene-loaded MOFs are discussed in the context of relevant porphyrin–fullerene donor–acceptor molecules to highlight the unique role of the framework environment in dictating photoinduced electron transfer and decay pathways.

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

Lone Pairs of Carbogenic Center Enable Thermally Activated Delayed Fluorescence from Carbon to Ligand Charge Transfer Excited States

Carbogenic compounds of the type L→C(0)←L, where L represents various ligands such as phosphines or carbenes, and C(0) denotes zerovalent carbon with two orthogonal lone pairs, are widely utilized in organic and coordination chemistry; however, in-depth photophysical and optical properties remain largely unknown. In the following work, we report detailed luminescent properties of one of the most prominent examples of carbogenic compounds, hexaphenylcarbodiphosphorane (CDP). Combined spectroscopic/TD-DFT studies demonstrate that both lone pairs of CDP participate in the observed visible light absorption and emission, which are associated with carbon lone pairs π*(PPh3) carbon to ligand charge transfer states (CLCTs). The CLCT exhibits a considerably decoupled electron-hole pair, resulting in a small S1-T1 gap and thermally assisted delayed fluorescence (TADF). Moreover, two lone pairs teamed up around C(0) provide numerous close-lying σ- and π-CLCT singlet and triplet states, which allow, for organic TADF emitters, extremely fast rates of exergonic intersystem crossing up to 1.27×109 s-1, competitive with some 3d and 4d metal-based TADF luminophores. These results open fresh directions for innovative design of novel luminescent materials for high-end photonic applications, utilizing lone pairs of carbogenic centers as donors of electron density in the excited states.

Mrózek, Ondřej [University of Southern California]↗
NASA NTRS2002

Near Infrared Emission of Highly Electronically Excited CO: A Sensitive Probe to Study the Interstellar Medium??

Among the various spectroscopic features of the second most abundant molecule in the space, CO, "the triplet - triplet transitions involving the lowest triplet state a(sup 3)II and the higher-lying a(sup 1)3 SIGMA (sup +), d(sup 3) (DELTA), e (sup 3) SIGMA (sup -) states spanning near-UV to mid-IR spectral range" have so far not been explored in astrophysical observations. The energies of these transitions are highly sensitive to the surroundings in which CO exists, i.e. gas-phase, polar or non-polar condensed phase. It is proposed here that these triplet-triplet emission/absorption bands can be used as a sensitive probe to investigate the local environments of CO, whether in the planetary atmosphere, stellar atmosphere or interstellar medium.

Gudipati, Murthy S.↗
DOE OSTI2024

Computation of the expectation value of the spin operator S^ 2 for the spin-flip Bethe–Salpeter equation

Spin-flip (SF) methods applied to excited-state approaches like the Bethe–Salpeter equation allow access to the excitation energies of open-shell systems, such as molecules and defects in solids. The eigenstates of these solutions, however, are generally not eigenstates of the spin operator S^ 2 . Even for simple cases where the excitation vector is expected to be, for example, a triplet state, the value of S^ 2 may be found to differ from 2.00; this difference is called 'spin contamination'. The expectation values S^ 2 must be computed for each excitation vector, to assist with the characterization of the particular excitation and to determine the amount of spin contamination of the state. Here, our aim is to provide for the first time in the SF methods literature a comprehensive resource on the derivation of the formulas for S^ 2 as well as its computational implementation. After a brief discussion of the theory of the SF Bethe–Salpeter equation (BSE) and some examples further illustrating the need for calculating S^ 2 , we present the derivation for the general equation for computing S^ 2 with the eigenvectors from an SF-BSE calculation, how it is implemented in a Python script, and timing information on how this calculation scales with the size of the SF-BSE Hamiltonian.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRSDate not supplied

Scalar Atomic Defect-Based Solid-State Self-calibrating Magnetometer (3SM) for Space Plasma Analysis

The Earth’s magnetosphere is a system of multiple, co-located particle populations interacting via plasma waves. Things to understand are driving processes, radiation belt and ring current issues, auroral physics, internal plasma processes, and magnetosphere-ionosphere mapping issues. These plasma-physics processes enable the Earth’s magnetosphere to evolve in response to temporal changes in the solar wind and they underlie the phenomena of space weather, which impacts spacecraft systems, astronauts, radio communications, and ground based electric-power grids. The objective of 3SM is to measure magnetic field strength and to calibrate the Vector Magnetometer (VM) device to maintain absolute accuracy during a mission. The 3SM features make the instrument preferably suited not only for the traditional role of scalar magnetometers as absolute references for the calibration of the on-board vector instruments, but also for extended operational capacities, such as higher frequency scalar measurements (of potential interest for magnetosphere studies for the low frequency part of the spectrum) or autonomous scalar / vector operations. Diamond has been the solid-state platform of choice for quantum device technologies for some time, however, it suffers from difficulties such as scalability, integration, and cost. While the diamond platform is very useful for quantum technologies, further development is needed to make it viable. The material platform of choice for NASA Glenn’s Quantum Sensing And Spin Physics (Q-SASP) is silicon carbide (SiC). This is due to the much higher industry development of the SiC material platform for high-power and high-temperature electronics. It leverages both the decades-long SiC development expertise and infrastructure at NASA Glenn and its growing capabilities in quantum metrology. To make SiC devices usable for quantum technologies such as quantum sources, a much deeper understanding of defects is needed. Q-SASP is developing quantum metrology capabilities to evaluate the energy structure, defect formation energy, band structure augmentation, generation/recombination rates, and limits of dipole-dipole coupling in non-metal implanted SiC devices. This can be achieved by analysis of zero-field splitting, low-field resonance, and singlet-triplet mixing through various forms of Electrically Detectable Magnetic Resonance (EDMR) and Near-Zero Field Magnetic Resonance (NZFMR) spectroscopy. This work will discuss recent system developments, device developments, computational modeling, and spectroscopy results and analysis of defects created by non-metal implantations in SiC devices. The defect formation energies of V Si ,V C , V C V Si , N C V Si , N Si , N C in 4H-SiC are previously reported values in other research [2]-[3]. The defect formation energies of PSi and PC were calculated in GPAW [fig 1A]. The basic underlying mechanism of the zero-field phenomenon is the mixing of singlet and triplet states [4]-[5]. In most spin-dependent transport, two electron spins are involved, and thus one must consider each of their interactions with the field. We investigated the electronic and magnetic properties of 4H-SiC and 6H-SiC. The defect formation energy helps us determine what types of defects we are observing in the SiC EDMR experiment. They have very low formation energy (it is negative). The phosphorus substitution in 4H-SiC is a very stable defect. The band diagrams provide us with vital information about how the electronic properties of SiC (such as band gap) change as we add non-metal defects. The zero-field splitting parameters allow us to study the inflection point in the NZFMR [fig 1B]. We clearly observed zero-field splitting. We also noted that the zero-field splitting remained constant with changing bias. We aspect it zero-field splitting to remain constant while the hyperfine and exchange interaction perturbations shift under the influence of an external magnetic field. This is the essence of quantum magnetometry and self-calibration.

space plasma↗
NASA NTRS2012

Free-Free Transitions of the e-H System Inside a Dense Plasma Irradiated by a Laser Field at Very Low Incident-Electron Energies

The free-free transition is studied for an electron-hydrogen atom in ground state when a low-energy electron (external) is injected into hydrogenic plasma in the presence of an external homogenous, monochromatic, and linearly polarized laser field. The effect of plasma screening is considered in the Debye-Huckel approximation. The calculations are performed in the soft photon limit. The incident electron is considered to be dressed by the laser field in a nonperturbative manner by choosing the Volkov solutions in both the initial and final channels. The space part of the scattering wave function for the electron is solved numerically by taking into account the electron exchange. The laser-assisted differential and total cross sections are calculated for single-photon absorption or emission and no-photon exchange in the soft photon limit, the laser intensity being much less than the atomic field intensity. The calculations have been carried out for various values of Debye parameter, ranging from 0.005 to 0.12. A strong suppression is noted in the laser-assisted cross sections as compared to the field-free situation. A significant difference is noted for the singlet and triplet cross sections. The suppression is much more in the triplet states.

Bhatia, A. K.↗
NASA NTRS2012

Free-Free Transitions of e-H System Inside a Dense Plasma Irradiated by a Laser Field at Very Low Incident Electron Energies

The free-free transition is studied for an electron-hydrogen in the ground state at low incident energies in the presence of an external homogenous, monochromatic, and linearly polarized laser-field inside a hot dense plasma.The effect of plasma screening is considered in the Debye-Huckel approximation. The calculations are performed in the soft photon limit, assuming that the plasma frequency is much higher than the laser frequency. The incident electron is considered to be dressed by the laser field in a nonperturbative manner by choosing the Volkov solutions in both the initial and final channels. The space part of the scattering wave function for the electron is solved numerically by taking into account the electron exchange. The laser-assisted differential and total cross sections are calculated for single-photon absorption /emission and no photon exchange in the soft photon limit, the laser intensity being much less than the atomic field intensity. The calculations have been carried out for various values of Debye parameter, ranging from 0.005 to 0.12. A strong suppression is noted in the laser-assisted cross sections as compared to the field-free situation. A significant difference is noted for the singlet and triplet cross sections. The suppression is much more in the triplet states.

Bhatia, A. K.↗
DOE OSTI2025

Molecular Mass Growth Processes to Polycyclic Aromatic Hydrocarbons through Radical–Radical Reactions Exploiting Photoionization Reflectron Time-of-Flight Mass Spectrometry

Polycyclic aromatic hydrocarbons (PAHs) represent critical building blocks in molecular mass growth processes to carbonaceous nanoparticles, referred to as interstellar and circumstellar grains along with soot particles in astrophysical environments and combustion systems, respectively. Recent advancements on elucidating elementary steps to PAHs have utilized reactions of aromatic radicals, resonantly stabilized free radicals, and aliphatic radicals with closed shell hydrocarbons. However, the role of radical–radical reactions (RRRs) leading to PAHs has remained largely unexplored on the molecular level due to preceding experimental challenges in producing sufficiently high number densities of radical reactants for isomer-selective detection of products from bimolecular and termolecular reactions. This Account offers the latest developments in our knowledge on the mechanisms and pathways to PAHs via RRRs probed in a chemical microreactor at temperatures as high as 1600 K. Product preservation in a molecular beam coupled with synchrotron vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry and photoelectron photoion coincidence spectroscopy enabled isomer-selective detection of PAHs of up to three rings by their photoionization efficiency curves, which were fit with a linear combination of reference curves for identification. Experiments were combined with computational fluid dynamics modeling of the physicochemical processes in the microreactor, as well as high-level electronic structure calculations to reveal the reaction pathways of each system. Six distinct reaction mechanisms were discovered in this work: propargyl addition─benzannulation (PABA), methyl addition─ring expansion (MARE), cyclopentadienyl addition─naphthylization (CPAN), fulvenallenyl addition─cyclization─aromatization (FACA), benzyl addition─aromatization (BAA), and phenyl addition─pentacyclization (PAP). By systematically varying the number of carbon atoms in the radical reactants, molecular mass growth processes involving reactions between radicals with odd numbers of carbon atoms access aromatics carrying one, two, or three six-membered rings, whereas reactions between even- and odd-carbon-numbered radicals produce aromatics combining five- and six-membered rings. Our investigations reveal unconventional cycloadditions on excited state triplet surfaces, additions of radicals to low spin density carbon-centered radicals, spiroaromatic and fulvene-type intermediates, and highly strained bicyclic reaction intermediates, challenging current perceptions of PAH molecular mass growth processes. All of the listed mechanisms, except for FACA, feature endoergic reactions or barriers which lie above the separated reactants and therefore might be central to circumstellar environments of carbon-rich stars and planetary nebulae as their descendants, but they play no role in the gas phase of cold molecular clouds where temperatures as low as 10 K dominate. Altogether, this work provides detailed reaction mechanisms of PAH growth processes, advancing our knowledge of the chemistry of carbonaceous matter in the universe.

Addition reactions↗
DOE OSTI2025

Light dark matter search with nitrogen-vacancy centers in diamonds

We propose an approach to directly search for light dark matter, such as the axion or the dark photon, by using magnetometry with nitrogen-vacancy centers in diamonds. If the dark matter couples to the electron spin, it affects the evolution of the Bloch vectors consisting of the spin triplet states, which may be detected through several magnetometry techniques. We give several concrete examples with the use of dc and ac magnetometry and estimate the sensitivity on dark matter couplings.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Generation of a fluorescent short-lifetime oxygen nanosensor by coupling of an exciplex forming dye pair

Typical oxygen-sensitive dyes have lifetimes in the μs-ms regime for sensitive oxygen detection based on molecular quenching. Due to the long triplet-state lifetimes and poor quenching efficiency of these probes, it has been difficult to develop short lifetime probes. We have developed oxygen sensors using a short-lifetime dye (∼30–60 ns) that forms an anthracene-aniline exciplex, which is quenched by molecular oxygen through an excited-state charge transfer mechanism. To achieve measurements in aqueous systems, we have tethered the dyes together via a C3 alkyl linker to facilitate greater exciplex formation at low dye concentration (20 μg mL −1 ) and encapsulated the resulting compound into polymeric nanoparticles to form an aqueous-dispersible short-lifetime oxygen nanosensor. The sensors emit at 420 nm (unfolded dye) and 500 nm (exciplex), and the ratiometric Stern-Volmer Constant is 1.52 ± 0.02 L mol −1 , showing good sensitivity from 0 % to 40 % dissolved oxygen without the tradeoff of a long lifetime needed for direct molecular quenching. In this paper, we characterize this sensor for both lifetime-based measurements using time-correlated single-photon counting and ratiometric intensity-based measurements using the unfolded dye emission as an internal reference peak.

Biological and medical sciences↗
DOE OSTI2025

Rhenium-Selenido Corroles: Reflections on 5d Metalloporphyrins and Metallocorroles as Triplet Emitters and Photosensitizers

Following the successful synthesis of rhenium-oxido, rhenium-imido, and rhenium-sulfido corroles, a series of para-X-substituted rhenium-selenido triarylcorroles (X = OCH 3 , CH 3 , H, F, CF 3 ) have been prepared in 70–76% yields. A one-pot, two-step procedure was used, analogous to that used for ReS corroles, involving rhenium insertion via high-temperature reaction of Re 2 (CO) 10 and free-base corroles in refluxing decalin, followed by exposure to PCl 3 (which is thought to deoxygenate ReO corroles formed under the reaction) and elemental selenium. An analogous procedure, however, failed to yield rhenium-tellurido corroles, presumably reflecting, according to DFT calculations, the limited stability of these species. Unlike ReO corroles, ReS and ReSe corroles were found not to exhibit phosphorescence in the NIR-I regime (600–1000 nm); nor did they sensitize singlet oxygen formation. In the hope of obtaining a broader perspective of this negative result, we also examined ReN porphyrins and found them not to phosphoresce or to sensitize singlet oxygen formation. These results were explained by DFT and TDDFT calculations in terms of low-energy triplet states, which are not energetic enough to excite molecular oxygen to its lowest singlet state. Whether some of the new Re corroles exhibit phosphorescence in the NIR-II regime remains an interesting question for future investigation.

Aromatic compounds↗
DOE OSTI2026

Syngas Production at Si Hybrid Photoelectrodes Modified with Re(I) and Mn(I) Tricarbonyl Phenanthroline Complexes Containing Reactive Aryl Azide Groups

We installed molecular CO 2 reduction (CO 2 R) catalysts directly onto Si (photo)electrodes. The highly reactive M(5-azido-1,10-phenanthroline)(CO) 3 X (where M = Mn or Re, X = Br or Cl) complexes readily bubbled when dissolved in polar organic solvents, in both the presence and absence of an ultraviolet light source. When placed on hydrogen-terminated Si (H-Si) and native silicon oxide (SiOx), similar amounts of the complex were attached to the surface under illumination (367 nm, 50–200 mW/cm 2 ) or in the dark. Surprisingly, these films revealed submonolayer coverages instead of the multilayered structures we expected. DFT analyses support monolayer formation, showing that the triplet-state nitrene of the complex is more energetically favorable than the singlet state. Using controlled-potential electrolysis experiments, we showed that Re- and Mn-containing films on pSi photoelectrodes generated small amounts of CO when exposed to 1 atm of CO 2 and 1 sun illumination. These amounts of CO were an order of magnitude greater than control surfaces, producing 5.59 × 10 –7 mol CO/h for Re(az-phen) and 7.83 × 10 –7 mol CO/h for Mn(az-phen) films. Much of the charge passed at the pSi electrodes was consumed by the competing hydrogen evolution reaction, which we attribute to the low molecular coverage and the presence of native oxide on the electrode surface after attachment. Finally, this work demonstrates the feasibility of reacting azide-containing ligands with Si surfaces. Still, it highlights the need for alternative ligand structures and reaction conditions to form multilayer films.

azides↗
NASA NTRS1970

The perturbation spectrum of CO

Perturbation rotational levels in triplet states of CO emission spectra attributed to resonance fluorescence process involving optically forbidden transitions

Black, G.↗
NASA NTRS1972

The IR emission spectrum of N2 excited under auroral conditions.

Recently determined experimental and theoretical cross sections for electron impact excitation of six triplet states of N2 (A, B, W, C, E, D) have been utilized to predict the absolute IR volume emission rates from N2 under nighttime auroral conditions. Secondary electron fluxes appropriate to an IBC II normal aurora were used in the calculations. The cascade contributions coupling the various electronic states were included as well as the most important quenching processes. The results indicate that the B yields reversibly A and W yields reversibly B cascade processes, which are important in the population of the A, B, and W states, produce appreciable radiation in the 1- to 5-micron wavelength region.

Cartwright, D. C.↗
NASA NTRS1976

Coordinated analysis of various auroral measurements made during NASA's 1968 and 1969 airborne auroral expeditions

Auroral optical measurements made aboard NASA's CV 990 were analyzed. The measurements analyzed form a small part of extensive spectroscopic, photometric and photographic data gathered during the 1968 and 1969 Airborne Auroral Expeditions. Simultaneous particle measurements from ESRO IA satellite were used in the analysis. Information about magnetospheric boundaries, interaction between magnetosheath particles and the terrestrial ionosphere, the polar bulge in helium abundance and excitation mechanisms of the triplet state of atmospheric N2 in auroras was obtained. Further analysis of the data is required to elucidate the relation between 3466 and 5200 A emissions of NI and the excitation of 3726-3729 A emissions from atomic oxygen ions in auroras.

Sivjee, G. G.↗