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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

The development and applications of multidimensional biomolecular spectroscopy illustrated by photosynthetic light harvesting

The parallel and synergistic developments of atomic resolution structural information, new spectroscopic methods, their underpinning formalism, and the application of sophisticated theoretical methods have led to a step function change in our understanding of photosynthetic light harvesting, the process by which photosynthetic organisms collect solar energy and supply it to their reaction centers to initiate the chemistry of photosynthesis. The new spectroscopic methods, in particular multidimensional spectroscopies, have enabled a transition from recording rates of processes to focusing on mechanism. We discuss two ultrafast spectroscopies – two-dimensional electronic spectroscopy and two-dimensional electronic-vibrational spectroscopy – and illustrate their development through the lens of photosynthetic light harvesting. Both spectroscopies provide enhanced spectral resolution and, in different ways, reveal pathways of energy flow and coherent oscillations which relate to the quantum mechanical mixing of, for example, electronic excitations (excitons) and nuclear motions. The new types of information present in these spectra provoked the application of sophisticated quantum dynamical theories to describe the temporal evolution of the spectra and provide new questions for experimental investigation. While multidimensional spectroscopies have applications in many other areas of science, we feel that the investigation of photosynthetic light harvesting has had the largest influence on the development of spectroscopic and theoretical methods for the study of quantum dynamics in biology, hence the focus of this review. We conclude with key questions for the next decade of this review.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Proximity-Induced Superconductivity in a 2D Kondo Lattice of an f -Electron-Based Surface Alloy

Realizing hybrids of low-dimensional Kondo lattices and superconducting substrates leads to fascinating platforms for studying the exciting physics of strongly correlated electron systems with induced superconducting pairing. Here, we report a scanning tunneling microscopy and spectroscopy study of a new type of two-dimensional (2D) La–Ce alloy grown epitaxially on a superconducting Re(0001) substrate. We observe the characteristic spectroscopic signature of a hybridization gap evidencing the coherent spin screening in the 2D Kondo lattice realized by the ultrathin La–Ce alloy film on normal conducting Re(0001). Upon lowering the temperature below the critical temperature of rhenium, a superconducting gap is induced exhibiting an energy asymmetry of the coherence peaks that arises from the interaction of residual unscreened magnetic moments with the superconducting substrate. A positive correlation between the Kondo hybridization gap and the asymmetry of the coherence peaks is found.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Local step-flow dynamics in thin film growth with desorption

Desorption of deposited species plays a role in determining the evolution of surface morphology during crystal growth when the desorption time constant is short compared with the time to diffuse to a defect site, step edge, or kink. However, experiments to directly test the predictions of these effects are lacking. Novel techniques such as in situ coherent x-ray scattering can provide significant new information. Herein we present x-ray photon correlation spectroscopy (XPCS) measurements during diindenoperylene (DIP) vapor deposition on thermally oxidized silicon surfaces. DIP forms a nearly complete two-dimensional first layer over the range of temperatures studied (40–120 ⁢°C), followed by mounded growth during subsequent deposition. Local step flow within mounds was observed, and we find that there was a terrace-length-dependent behavior of the step edge dynamics. This led to unstable growth with rapid roughening (β>0.5) and deviation from a symmetric error-function-like height profile. At high temperatures, the grooves between the mounds tend to close up leading to nearly flat polycrystalline films. In conclusion, numerical analysis based on a (1+1)-dimensional model suggests that terrace-length dependent desorption of deposited ad-molecules is an essential cause of the step dynamics, and it influences the morphology evolution.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Terahertz stimulated parametric downconversion of a magnon mode in an antiferromagnet

Parametric amplification, where one signal is enhanced by the action of another, offers both practical utility for boosting weak signals and fundamental insights into the nonlinear coupling between degrees of freedom. In condensed matter systems, interactions between collective modes offer avenues for nonlinear coherent manipulation of coupled excitations and quantum phases. Antiferromagnets, with inherently coupled magnon modes, provide a promising platform for nonlinear control of spin waves and magnetization. However, nonlinear magnon-magnon interactions have been only partially elaborated, leaving key gaps in the prospects for potential ultrahigh-bandwidth magnonic signal processing. Here, we excite two distinct coherent magnon modes in an antiferromagnet and find that the magnon mode with a lower frequency undergoes amplification when the higher-frequency mode is driven. We unveil the nonlinear excitation pathways of this stimulated parametric downconversion process by using polarization-selective two-dimensional terahertz spectroscopy. Our work provides fundamental insights into nonlinear magnonics in antiferromagnets, laying the groundwork for forthcoming spintronic and magnonic devices.

Science & Technology - Other Topics↗
DOE OSTI2023

Quantum dynamics simulations of the 2D spectroscopy for exciton polaritons

We develop an accurate and numerically efficient non-adiabatic path-integral approach to simulate the non-linear spectroscopy of exciton–polariton systems. This approach is based on the partial linearized density matrix approach to model the exciton dynamics with explicit propagation of the phonon bath environment, combined with a stochastic Lindblad dynamics approach to model the cavity loss dynamics. Through simulating both linear and polariton two-dimensional electronic spectra, we systematically investigate how light–matter coupling strength and cavity loss rate influence the optical response signal. Our results confirm the polaron decoupling effect, which is the reduced exciton–phonon coupling among polariton states due to the strong light–matter interactions. We further demonstrate that the polariton coherence time can be significantly prolonged compared to the electronic coherence outside the cavity.

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

Ultrafast Carrier Self-Trapping Driven by Strong Exciton–Phonon Coupling in 2D MA 3 Bi 2 I 6 Cl 3 Perovskite

Two-dimensional (2D) hybrid bismuth halide perovskites have emerged as promising lead-free materials for optoelectronic applications due to their solution processability and tunable structures. Here, in this study, we investigate 2D layered hybrid perovskite MA 3 Bi 2 I 6 Cl 3 using temperature-dependent photoluminescence (PL) and femtosecond transient absorption spectroscopy. Our results reveal strong coupling between excitons and phonons, evidenced by giant Huang–Rhys factors, coherent phonon oscillations, and ultrafast carrier self-trapping into small-polaron and self-trapped exciton (STE) states. These processes appear as time-dependent ground-state bleach and photoinduced absorption features, highlighting the influence of the lattice in carrier dynamics. Wavelength- and time-resolved measurements reveal that PL emission is dominated by STEs, while free exciton emission is weak and short-lived. By comparing 2D MA 3 Bi 2 I 6 Cl 3 with 0D MA 3 Bi 2 I 9 , which contains molecularly isolated [BiI 6 ] 3− octahedra and 2D MA 3 Bi 2 Br 9 perovskites, we demonstrate how halide composition and structural dimensionality influence the balance between free exciton populations and carrier localization. These insights uncover the intrinsic kinetic landscape of photoexcited states in MA 3 Bi 2 I 6 Cl 3 . Overall, our study contributes to a mechanistic understanding of exciton–phonon interactions in lead-free 2D perovskites.

Pradeep, Kodimana Ramakrishnan [Northwestern Univ.↗
DOE OSTI2024

Solution-phase sample-averaged single-particle spectroscopy of quantum emitters with femtosecond resolution

Here, the development of many optical quantum technologies depends on the availability of solid-state single quantum emitters with near-perfect optical coherence. However, a standing issue that limits systematic improvement is the significant sample heterogeneity and lack of mechanistic understanding of microscopic energy flow at the single emitter level and ultrafast timescales. Here we develop solution-phase single-particle pump-probe spectroscopy with photon correlation detection that captures sample-averaged dynamics in single molecules and/or defect states with unprecedented clarity at femtosecond resolution. We apply this technique to single quantum emitters in two-dimensional hexagonal boron nitride, which suffers from significant heterogeneity and low quantum efficiency. From millisecond to nanosecond timescales, the translation diffusion, metastable-state-related bunching shoulders, rotational dynamics, and antibunching features are disentangled by their distinct photon-correlation timescales, which collectively quantify the normalized two-photon emission quantum yield. Leveraging its femtosecond resolution, spectral selectivity and ultralow noise (two orders of magnitude improvement over solid-state methods), we visualize electron-phonon coupling in the time domain at the single defect level, and discover the acceleration of polaronic formation driven by multi-electron excitation. Corroborated with results from a theoretical polaron model, we show how this translates to sample-averaged photon fidelity characterization of cascaded emission efficiency and optical decoherence time. Our work provides a framework for ultrafast spectroscopy in single emitters, molecules, or defects prone to photoluminescence intermittency and heterogeneity, opening new avenues of extreme-scale characterization and synthetic improvements for quantum information applications.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Spectral broadening and vibronic dynamics of the S2 state of canthaxanthin in the orange carotenoid protein

We have performed a series of broadband multidimensional electronic spectroscopy experiments to probe the electronic and vibrational dynamics of the canthaxanthin chromophore of the Orange Carotenoid Protein (OCP) from Synechocystis sp. PCC 6803 in its photoactivated red state, OCPR. Cross-peaks observed below the diagonal of the two-dimensional electronic spectrum indicate that absorption transitions prepare the bright S2 state of the ketocarotenoid canthaxanthin near to a sequence of conical intersections, allowing passage to the dark S1 state via the Sx intermediate in <50 fs. Rapid damping of excited-state coherent wavepacket motions suggests that the branching coordinates of the conical intersections include out-of-plane deformation and C=C stretching coordinates of the π-conjugated isoprenoid backbone. The unusual proximity of the Franck–Condon S2 state structure to the conical intersections with Sx and S1 suggests that the protein surroundings of canthaxanthin prepare it to function as an excitation energy trap in the OCPR–phycobilisome complex. Numerical simulations using the multimode Brownian oscillator model demonstrate that the ground-state absorption spectrum of OCPR overlaps with the fluorescence emission spectrum of allophycocyanin due to spectral broadening derived especially from the intramolecular motions of the canthaxanthin chromophore in its binding site.

Yang, Kunwei↗
DOE OSTI2023

Final Report

This project focused on investigating the prospects of two-dimensional (2D) materials, transition metal dichalcogenides (TMDs) and graphene, for developing nanostructures that are potentially useful for quantum science. These materials class exhibit a range of fascinating electronic and optical properties and, due to their sub-nanometer thickness, are particularly well suited for confining electronic quantum states in atomic-size structures. The project involved developing first-principles calculations that can predict coherent lifetimes of defects; theoretical schemes for identifying new platforms suitable for studying the dynamics of driven quantum systems; and optical and electronic spectroscopy characterization of novel defects and heterostructures with the aim of creating the next generation of materials for quantum science. This report provides a brief background into the project, highlights some of the major achievements accomplished within the projects and lists the supported publications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2026

Long-lived polaritonic coherence and polaron decoupling effects in 2D electronic spectra

Molecular polaritons, formed by coupling molecular excitons with cavity photons, offer a promising platform for exploring quantum phenomena. A key challenge is understanding how these hybrid states maintain coherence in the presence of environmental vibrations. Here, we show theoretically that collective coupling of many molecular excitons in a cavity can protect polariton coherence from phonon-induced decoherence. Under realistic conditions, the coherence time can extend up to 200 fs at room temperature, compared with 15 fs for typical molecular systems. Simulations of two-dimensional electronic spectra reveal prolonged oscillations between upper and lower polariton states, and reduced vibrational coupling as indicated by changes in the nodal line slope of the lower polariton peak. These findings provide guidance for experimental efforts to realize long-lived polaritons, such as coupling CdSe nanoplatelets to optical cavities.

2D electronic spectroscopy↗
DOE OSTI2024

Observation of interlayer plasmon polaron in graphene/WS 2 heterostructures

Harnessing electronic excitations involving coherent coupling to bosonic modes is essential for the design and control of emergent phenomena in quantum materials. In situations where charge carriers induce a lattice distortion due to the electron-phonon interaction, the conducting states get “dressed", which leads to the formation of polaronic quasiparticles. The exploration of polaronic effects on low-energy excitations is in its infancy in two-dimensional materials. Here, we present the discovery of an interlayer plasmon polaron in heterostructures composed of graphene on top of single-layer WS 2 . By using micro-focused angle-resolved photoemission spectroscopy during in situ doping of the top graphene layer, we observe a strong quasiparticle peak accompanied by several carrier density-dependent shake-off replicas around the single-layer WS 2 conduction band minimum. Our results are explained by an effective many-body model in terms of a coupling between single-layer WS 2 conduction electrons and an interlayer plasmon mode. It is important to take into account the presence of such interlayer collective modes, as they have profound consequences for the electronic and optical properties of heterostructures that are routinely explored in many device architectures involving 2D transition metal dichalcogenides.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Decoherence of V B spin defects in monoisotopic hexagonal boron nitride

Spin defects in hexagonal boron nitride (hBN) are promising quantum systems for the design of flexible two-dimensional quantum sensing platforms. Here we rely on hBN crystals isotopically enriched with either 10B or 11B to investigate the isotope-dependent properties of a spin defect featuring a broadband photoluminescence signal in the near infrared. By analyzing the hyperfine structure of the spin defect while changing the boron isotope, we first unambiguously confirm that it corresponds to the negatively-charged boron-vacancy center (V− B ). We then show that its spin coherence properties are slightly improved in 10B-enriched samples. This is supported by numerical simulations employing cluster correlation expansion methods, which reveal the importance of the hyperfine Fermi contact term for calculating the coherence time of point defects in hBN. Using crossrelaxation spectroscopy, we finally identify dark electron spin impurities as an additional source of decoherence. This work provides new insights into the properties of V− B spin defects, which are valuable for the future development of hBN-based quantum sensing foils.

Haykal, A.↗
DOE OSTI2025

Spectral broadening and pulse shaping in the deep ultraviolet

Here, we report the generation and shaping of ∼20 femtosecond pulses in the deep ultraviolet (DUV). Our approach combines spectral broadening in a stretched hollow-core fiber with compression and shaping via an acousto-optic modulator-based pulse shaper. The pulse shaper allows for automatic compression, useful for in-air delivery of pulses to two-dimensional (2D) spectroscopy and other time-resolved experiments. Unlike previous DUV pulse generation schemes that lack phase stability, our method enables programmable generation of phase-locked pulse-pairs with attosecond-level stability. We demonstrate pulse characterization via self-diffraction frequency-resolved optical gating and dispersion scan methods in the DUV and validate performance through a pump-probe experiment resolving electronic dynamics on attosecond timescales.

Codere, Julia [Stony Brook Univ., NY (United State↗
DOE OSTI2026

Direct Observation of Ultrafast Defect-Bound and Free Exciton Dynamics in Defect-Engineered WS 2 Monolayers

Defects in two-dimensional transition metal dichalcogenides (TMDCs) broadly affect their optical and electronic properties. Directly capturing the ultrafast processes of exciton trapping and defect-bound exciton formation is crucial for understanding and advancing defect-mediated optoelectronics and quantum technologies. However, the weak transient optical absorption of defect-bound excitons has limited their experimental observation to date. Here, we report the direct observation of the ultrafast dynamics of defect-bound excitons in monolayer WS 2 crystals with a high density of monosulfur vacancies (V S ) and W-site defect complexes (S W V S ) resulting from synthesis by alkali metal halide-assisted chemical vapor deposition. The dynamics of excitons bound to these defects, along with their coherent interactions with free excitons, are elucidated using ultrafast optical spectroscopy. Using above band-edge photoexcitation, we find that both free and defect-bound excitons simultaneously form within 300 fs from hot carrier relaxation. The defect-bound excitons exhibit shorter lifetimes than free excitons, leading to a population difference of the corresponding excitonic states and free exciton trapping within a 1–100 ps window. Band-edge photoexcitation of free and defect-bound exciton states reveals ultrafast interconversion within ∼150 fs (comparable to our temporal resolution), indicating possible coherent coupling between these states. We further demonstrate efficient up-conversion of defect-bound excitons to free excitons with photon energies up to ∼300 meV below the free exciton resonance. In conclusion, these findings provide insights into the ultrafast dynamics of defect-bound excitons in TMDCs and their coupling with free excitons, which are relevant to defect-engineered optoelectronic, quantum photonic, and valleytronic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Hourglass-type bulk Ni 3 d band and Ce 4 f Kondo resonance states in the potential topological Kondo semimetal CeNiSn via angle-resolved photoemission spectroscopy

The electronic structure of CeNiSn, which is a potential topological Kondo insulator and a Dirac nodal-loop semimetal, has been investigated by employing temperature (T) dependent angle-resolved photoemission spectroscopy (ARPES). The Fermi surfaces (FSs) and the band structures of CeNiSn for three orthogonal crystallographic planes are measured, in which both the very dispersive bands and the flat bands are observed, having mainly the Ni 3d character and the Ce 4f character, respectively. The measured FSs and ARPES bands agree reasonably well with the density functional theory (DFT) calculations. The Fermi-edge (E F ) photon energy (hν) map along k b (=k (010) ) shows that the metallic E F -crossing states on the (010) surface have the three-dimensional character, suggesting that the observed E F -crossing metallic states do not correspond to the topological surface states of the two-dimensional character. On the other hand, albeit weak, the features of the hourglass-type bulk band crossings are observed along SXS, with the energies and the slopes being similar to those predicted by the DFT calculations, supporting the Dirac semimetallic nature of CeNiSn. In T-dependent ARPES, the Ce 4f Kondo resonance states are clearly revealed at low T, which become much suppressed above ~80 K. This feature is consistent with the Kondo temperature of CeNiSn, estimated from its ρ(T) data. This work demonstrates the importance of the coherent Kondo states in determining the topological properties of CeNiSn.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Stretched exponential magnetic relaxation dynamics in artificial square ice revealed through x-ray photon correlation spectroscopy

X-ray photon correlation scattering measurements are undertaken on a thermally active artificial spin ice based on the square lattice, referred to as artificial square ice, to probe the fluctuation timescales as a function of temperature as the system passes through the paramagnetic-antiferromagnetic phase transition, which belongs to the two-dimensional Ising universality class. In the paramagnetic regime, a single exponential timescale is seen, whereas at and below the critical temperature, a stretched exponential decorrelation is observed, with the stretching exponent decreasing from unity down to below one-half as the temperature reduces. This trend is confirmed by kinetic Monte Carlo simulations of a simplified point-dipolar square ice system, and is in agreement with past theoretical work on the kinetic Ising model where stretched exponential relaxation due to equilibrium domain wall dynamics below the critical temperature was found.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Strain-induced topological transitions in epitaxial films of cadmium arsenide

Strain in epitaxial thin films can have a profound influence on their electronic bands. Here, we investigate the influence of epitaxial strains on the electronic states of (001)-oriented cadmium arsenide (Cd 3 As 2 ) thin films, which are two-dimensional topological insulators. Cd 3 As 2 films were grown coherently on Al 1−x In x Sb buffer layers with varying degrees of lattice mismatch to Cd 3 As 2 , producing in-plane stresses that ranged from compressive to tensile. Using magneto-transport measurements of the Landau levels of the lowest subbands, we show that films under compression remain in the two-dimensional topological insulator state, while a sufficiently large tensile stress induces a transition to a topologically trivial phase. These results qualitatively agree with expectations from theoretical models for these films. At the topological transition, the gap avoids completely closing, and we discuss possible origins.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Distinct vibrational motions promote disparate excited-state decay pathways in cofacial perylenediimide dimers

A complex interplay of structural, electronic, and vibrational degrees of freedom underpins the fate of molecular excited states. Organic assemblies exhibit a myriad of excited-state decay processes, such as symmetry-breaking charge separation (SB-CS), excimer (EX) formation, singlet fission, and energy transfer. Recent studies of cofacial and slip-stacked perylene-3,4:9,10-bis(dicarboximide) (PDI) multimers demonstrate that slight variations in core substituents and H- or J-type aggregation can determine whether the system follows an SB-CS pathway or an EX one. However, questions regarding the relative importance of structural properties and molecular vibrations in driving the excited-state dynamics remain. Here, we use a combination of two-dimensional electronic spectroscopy, femtosecond stimulated Raman spectroscopy, and quantum chemistry computations to compare the photophysics of two PDI dimers. The dimer with 1,7-bis(pyrrolidin-1′-yl) substituents (5PDI2) undergoes ultrafast SB-CS from a photoexcited mixed state, while the dimer with bis-1,7-(3′,5′-di-t-butylphenoxy) substituents (PPDI2) rapidly forms an EX state. Examination of their quantum beating features reveals that SB-CS in 5PDI2 is driven by the collective vibronic coupling of two or more excited-state vibrations. In contrast, we observe signatures of low-frequency vibrational coherence transfer during EX formation by PPDI2, which aligns with several previous studies. We conclude that key electronic and structural differences between 5PDI2 and PPDI2 determine their markedly different photophysics.

Chemistry↗