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DOE OSTI2025

Dissipation Pathways in a Photosynthetic Complex

Determining how energy flows within and between molecules is crucial for understanding chemical reactions, material properties, and even vital processes such as photosynthesis. While the general principles of energy transfer are well established, elucidating the specific molecular pathways by which energy is funneled remains challenging, as it requires tracking energy flow in complex molecular environments. Here, we demonstrate how photon excitation energy is partially dissipated in the light-harvesting Fenna–Matthews–Olson (FMO) complex, mediating the excitation energy transfer from light-harvesting chlorosomes to the photosynthetic reaction center in green sulfur bacteria. Specifically, we isolate the contribution of the protein and specific vibrational modes of the pigment molecules to the energy dynamics. For this, we introduce an efficient computational implementation of a recently proposed theory of dissipation pathways for open quantum systems, based on second-order perturbation theory in the electronic couplings. Using it and a state-of-the-art FMO model with highly structured and chromophore-specific spectral densities, we demonstrate that energy dissipation is dominated by low-frequency modes (<800 cm –1 ) as their energy range is near-resonance with the energy gaps between electronic states of the pigments. We identify the most important modes for dissipation to be in-plane breathing modes (∼200 cm –1 ) of the bacteriochlorophylls in the complex. Conversely, far-detuned intramolecular vibrations with higher frequencies (>800 cm –1 ) play no role in dissipation. Interestingly, the FMO complex first needs to borrow energy from the environment to release excess photonic energy, indicating that the energy exchange between the system and thermal environment is not strictly unidirectional in time but involves a transient thermally activated step. Beyond their fundamental value, these insights can guide the development of artificial light-harvesting devices and, more broadly, engineer environments for chemical and quantum control tasks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Excited-state electronic structure of molecules using many-body Green’s functions: Quasiparticles and electron–hole excitations with VOTCA-XTP

Here, we present the open-source VOTCA-XTP software for the calculation of the excited-state electronic structure of molecules using many-body Green’s function theory in the GW approximation with the Bethe–Salpeter equation (BSE). This work provides a summary of the underlying theory and discusses the details of its implementation based on Gaussian orbitals, including resolution-of-identity techniques and different approaches to the frequency integration of the self-energy or acceleration by offloading compute-intensive matrix operations using graphics processing units in a hybrid OpenMP/Cuda scheme. A distinctive feature of VOTCA–XTP is the capability to couple the calculation of electronic excitations to a classical polarizable environment on an atomistic level in a coupled quantum- and molecular-mechanics (QM/MM) scheme, where a complex morphology can be imported from Molecular Dynamics simulations. The capabilities and limitations of the GW–BSE implementation are illustrated with two examples. First, we study the dependence of optically active electron–hole excitations in a series of diketopyrrolopyrrole-based oligomers on molecular-architecture modifications and the number of repeat units. Second, we use the GW–BSE/MM setup to investigate the effect of polarization on localized and intermolecular charge-transfer excited states in morphologies of low-donor content rubrene–fullerene mixtures. These showcases demonstrate that our implementation currently allows us to treat systems with up to 2500 basis functions on regular shared-memory workstations, providing accurate descriptions of quasiparticle and coupled electron–hole excited states of various characters on an equal footing.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2026

Transitions, Dynamics, and Driven States in Quantum Magnets (Final Report Revised)

Transitions into unusual electronic, optical, and magnetic states at the absolute zero of temperature display special properties that teach us about fundamental quantum mechanics and also underlie important technologies. These so-called quantum phase transitions intertwine the static and dynamical responses of the materials changing state. They are extremely sensitive to the effects of disorder and etch in high relief the role of quantum fluctuations. There are ample questions remaining about the character of such transitions and the nature of the competing quantum states. There are also opportunities to drive quantum materials out of equilibrium, with the possibility of new types of correlated and coherent order, and new ways to access the dynamical evolution of ground and excited states. We have investigated how the order develops in time and space, and the nature of the final configurations. We are able to compare and contrast classical and quantum excitations in our experimental system of choice, and thereby can trace the relative speed by which the system settles into its lowest-energy ground state. This comparison of quantum and classical annealing protocols lies at the heart of strategies for harnessing the power of quantum computers dedicated to optimization problems. A combination of magnetic susceptibility measurements at finite frequency where the magnetic spins are queried by an external ac field, dc magnetometry measurements that characterize the macroscopic strength of magnetic order and its resistance to change, noise measurements that reveal the microscopic fluctuations of the spins as they prepare to change state, and microwave spectroscopy to look at the response of both the electronic and nuclear degrees of freedom, have been performed as functions of temperature, magnetic field, frequency, excitation amplitude, magnetic spin concentration, and disorder. This combination of probes addresses issues of stability over time, overlap between spin states, the ability of the spins to respond independently or coherently, and the promise of control on the nanometer length scale. The research reported here provides insights into fundamental quantum physics. It also addresses the question of how best to use complex systems, such as magnetic solids, to stably process quantum information.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2020

Vibronic mixing enables ultrafast energy flow in light-harvesting complex II

Since the discovery of quantum beats in the two-dimensional electronic spectra of photosynthetic pigment-protein complexes over a decade ago, the origin and mechanistic function of these beats in photosynthetic light-harvesting has been extensively debated. The current consensus is that these long-lived oscillatory features likely result from electronic-vibrational mixing, however, it remains uncertain if such mixing significantly influences energy transport. Here, we examine the interplay between the electronic and nuclear degrees of freedom (DoF) during the excitation energy transfer (EET) dynamics of light-harvesting complex II (LHCII) with two-dimensional electronic-vibrational spectroscopy. Particularly, we show the involvement of the nuclear DoF during EET through the participation of higher-lying vibronic chlorophyll states and assign observed oscillatory features to specific EET pathways, demonstrating a significant step in mapping evolution from energy to physical space. These frequencies correspond to known vibrational modes of chlorophyll, suggesting that electronic-vibrational mixing facilitates rapid EET over moderately size energy gaps.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Excitation-dependent features and artifacts in 2-D terahertz spectroscopy

Recently, two-dimensional terahertz spectroscopy (2DTS) has attracted increasing attention for studying complex solids. A number of recent studies have applied 2DTS either with long pulses or away from any material resonances, situations that yield unconventional 2DTS spectra that are often difficult to interpret. Here, we clarify the generic origins of observed spectral features by examining 2DTS spectra of ZnTe, a model system with a featureless optical susceptibility at low terahertz frequencies. These results also reveal possible artifacts that may arise from electro-optic sampling in collinear 2DTS experiments, including the observation of spurious rectified or second harmonic signals.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2023

An efficient protocol for excited states of large biochromophores

Efficient energy transport in photosynthetic antenna is a long-standing source of inspiration for artificial light harvesting materials. However, characterizing the excited states of the constituent chromophores poses a considerable challenge to mainstream quantum chemical and semiempirical excited state methods due to their size and complexity and the accuracy required to describe small but functionally important changes in their properties. In this paper, we explore an alternative approach to calculating the excited states of large biochromophores, exemplified by a specific method for calculating the Q y transition of bacteriochlorophyll a, which we name Chl-xTB. Using a diagonally dominant approximation to the Casida equation and a bespoke parameterization scheme, Chl-xTB can match time-dependent density functional theory’s accuracy and semiempirical speed for calculating the potential energy surfaces and absorption spectra of chlorophylls. We demonstrate that Chl-xTB (and other prospective realizations of our protocol) can be integrated into multiscale models, including concurrent excitonic and point-charge embedding frameworks, enabling the analysis of biochromophore networks in a native environment. We exploit this capability to probe the low-frequency spectral densities of excitonic energies and interchromophore interactions in the light harvesting antenna protein LH2 (light harvesting complex 2). The impact of low-frequency protein motion on interchromophore coupling and exciton transport has routinely been ignored due to the prohibitive costs of including it in simulations. Our results provide a more rigorous basis for continued use of this approximation by demonstrating that exciton transition energies are unaffected by low-frequency vibrational coupling to exciton interaction energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Nonlinear ionization dynamics of hot dense plasma observed in a laser-plasma amplifier

Understanding the behaviour of matter under conditions of extreme temperature, pressure, density and electromagnetic fields has profound effects on our understanding of cosmologic objects and the formation of the universe. Lacking direct access to such objects, our interpretation of observed data mainly relies on theoretical models. However, such models, which need to encompass nuclear physics, atomic physics and plasma physics over a huge dynamic range in the dimensions of energy and time, can only provide reliable information if we can benchmark them to experiments under well-defined laboratory conditions. Due to the plethora of effects occurring in this kind of highly excited matter, characterizing isolated dynamics or obtaining direct insight remains challenging. High-density plasmas are turbulent and opaque for radiation below the plasma frequency and allow only near-surface insight into ionization processes with visible wavelengths. Here, the output of a high-harmonic seeded laser-plasma amplifier using eight-fold ionized krypton as the gain medium operating at a 32.8 nm wavelength is ptychographically imaged. A complex-valued wavefront is observed in the extreme ultraviolet (XUV) beam with high resolution. Ab initio spatio-temporal Maxwell–Bloch simulations show excellent agreement with the experimental observations, revealing overionization of krypton in the plasma channel due to nonlinear laser-plasma interactions, successfully validating this four-dimensional multiscale model. This constitutes the first experimental observation of the laser ion abundance reshaping a laser-plasma amplifier. The presented approach shows the possibility of directly modelling light-plasma interactions in extreme conditions, such as those present during the early times of the universe, with direct experimental verification.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Large Area Detection of Microstructural Defects with Multi-Mode Ultrasonic Signals

Cyclic loading or other stresses can lead to development of cracks and crack growth in mechanical structures, leading to eventual failure. While ultrasound imaging can be used for non-destructive testing of such structures, conventional ultrasound techniques are often limited by crack size, density, and areal coverage. An effective characterization of real-world, large-area structures is required at an early damage stage to prevent catastrophic failure and predict remaining life. In this study, a new nonlinear ultrasonic testing (NUT) method is proposed for large-area monitoring of practical structures with arbitrary complexity by using multiple-mode guided-wave ultrasonic signals. The proposed guided-wave NUT technique requires single-element transducers, simple electronics, and a mixed time-frequency domain signal processing. As a proof-of-concept demonstration, numerical simulations and experiments are performed on an A36 carbon steel beam assembly with previously formed microstructural defects that cause nonlinearities in ultrasonic response. The quadratic dependence of the nonlinear wave excitation on the input ultrasonic signal amplitude is shown by numerical simulations, and such a nonlinear ultrasonic response is experimentally observed in the zone with a high density of microstructural defects.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Chirped Laser Pulse Control of Vibronic Wavepackets and Energy Transfer in Phycocyanin 645

Photosynthetic organisms use light-harvesting complexes to increase the spectrum of light that they absorb from solar photons. Recent ultrafast spectroscopic studies have revealed that efficient (sub-ps) energy transfer is mediated by vibronic coherence in the phycobiliprotein phycocyanin 645 (PC645). Here, we report studies that employ broadband pump–probe spectroscopy with linearly chirped excitation pulses to further investigate the relationship between vibronic state preparation and energy transfer dynamics in PC645. Negatively chirped pulse excitation is found to enhance wavepackets of a high-frequency mode (1580 cm –1 ) and increase the rate of downhill energy transfer, while on the other hand, positively chirped pulses suppress these oscillatory features and decrease this rate. Model calculations incorporating the influence of the chirped pump pulse are used to understand its effect on initial state preparation. Furthermore, these results provide mechanistic insight into how the overall nonequilibrium rate of energy transfer is influenced by initial state preparation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Adaptive Critical Balance and Firehose Instability in an Expanding, Turbulent, Collisionless Plasma

Abstract Using a hybrid-kinetic particle-in-cell simulation, we study the evolution of an expanding, collisionless, magnetized plasma in which strong Alfvénic turbulence is persistently driven. Temperature anisotropy generated adiabatically by the plasma expansion (and consequent decrease in the mean magnetic-field strength) gradually reduces the effective elasticity of the field lines, causing reductions in the linear frequency and residual energy of the Alfvénic fluctuations. In response, these fluctuations modify their interactions and spatial anisotropy to maintain a scale-by-scale “critical balance” between their characteristic linear and nonlinear frequencies. Eventually the plasma becomes unstable to kinetic firehose instabilities, which excite rapidly growing magnetic fluctuations at ion-Larmor scales. The consequent pitch-angle scattering of particles maintains the temperature anisotropy near marginal stability, even as the turbulent plasma continues to expand. The resulting evolution of parallel and perpendicular temperatures does not satisfy double-adiabatic conservation laws, but is described accurately by a simple model that includes anomalous scattering. Our results have implications for understanding the complex interplay between macro- and microscale physics in various hot, dilute, astrophysical plasmas, and offer predictions concerning power spectra, residual energy, ion-Larmor-scale spectral breaks, and non-Maxwellian features in ion distribution functions that may be tested by measurements taken in high-beta regions of the solar wind.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2026

Vibrational Spin-Orbit Coupling Contributions to Excited State Decay of Ligand-to-Ligand Charge Transfer States

Controlling excited state relaxation processes is important in a variety of photochemical and photophysical processes, including the generation of ground and excited state spin polarization for quantum information science applications. Here, we address how specific static distortions – based on vibrational spin-orbit active modes at C2v symmetry determined by group theory – in a series of low-symmetry ligand-to-ligand charge transfer complexes enable direct spin-orbit coupling contributions to T1 → S0 excited state decay. These results are used to address spin-vibronic coupling contributions to T1 → S0 decay in a high-symmetry (tBu2bpy)Pt(S,S) (tBu2bpy = 4,4’-di-tert-butyl-2,2’-bipyridine and S,S = benzene-1,2-dithiolate) ligand-to-ligand charge transfer complex with effective C2v symmetry, where T1 relaxation is both spin- and orbitally forbidden due to the direct spin-orbit coupling matrix element being zero by symmetry. Low-frequency vibrations that involve a pyridine-pyridine twisting motion within the bpy ligand generate large ∂/∂Qi values that will contribute significantly to T1 → S0 relaxation. The work advances ligand design strategies for the generation of tailored T1 → S0 relaxation rates, which can be utilized to optimize the generation of electron spin polarization in radical-elaborated ligand-to-ligand charge transfer complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Nonlinear Characterization of a Joint Exhibiting a Reduction in Damping at High Energy

Even with the advent of additive manufacturing, the vast majority of complex structures are comprised of individual components held together with bolted joints. However, bolted joints present a challenge for mechanical design as they are a source of nonlinearity and increase the uncertainty in the overall behavior of the system in a dynamic environment. While many advances have been made in the ability to accurately model and test bolted joints, it is still an open area of research. Modes of vibration that exercise bolted joints typically exhibit nonlinear behavior where, with increased excitation level, the natural frequency decreases (i.e. softens) and the damping increases. However, the system under study for this work has an axial mode which does not follow this trend; it does soften as expected, but, after an initial increase, the apparent damping decreases with excitation amplitude. At the highest excitation level, the frequency of the mode decreases to that of a nearby bending mode and the response is amplified nearly 500% above that at lower levels. It is unclear whether the decrease in damping is due to the coupling of the two modes or if it is a characteristic of the axial mode. Therefore, the objective of this project is to investigate the coupling between the axial and bending modes and the dynamics leading to the decrease in damping.

42 ENGINEERING↗

DOE OSTI2021

Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer

It is well known that the solvent plays a critical role in ultrafast electron-transfer reactions. However, solvent reorganization occurs on multiple length scales, and selectively measuring short-range solute–solvent interactions at the atomic level with femtosecond time resolution remains a challenge. Here we report femtosecond X-ray scattering and emission measurements following photoinduced charge-transfer excitation in a mixed-valence bimetallic (Fe ii Ru iii ) complex in water, and their interpretation using non-equilibrium molecular dynamics simulations. Combined experimental and computational analysis reveals that the charge-transfer excited state has a lifetime of 62 fs and that coherent translational motions of the first solvation shell are coupled to the back electron transfer. Overall, our molecular dynamics simulations identify that the observed coherent translational motions arise from hydrogen bonding changes between the solute and nearby water molecules upon photoexcitation, and have an amplitude of tenths of ångströms, 120–200 cm -1 frequency and ~100 fs relaxation time. This study provides an atomistic view of coherent solvent reorganization mediating ultrafast intramolecular electron transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Exciton polaron formation and hot-carrier relaxation in rigid Dion–Jacobson-type two-dimensional perovskites

The efficiency of two-dimensional Dion–Jacobson-type materials relies on the complex interplay between electronic and lattice dynamics; however, questions remain about the functional role of exciton–phonon interactions. Here we establish the robust polaronic nature of the excitons in these materials at room temperature by combining ultrafast spectroscopy and electronic structure calculations. We show that polaronic distortion is associated with low-frequency (30–60 cm –1 ) lead iodide octahedral lattice motions. More importantly, we discover how targeted ligand modification of this two-dimensional perovskite structure manipulates exciton–phonon coupling, exciton polaron population and carrier cooling. At high excitation density, stronger exciton–phonon coupling increases the hot-carrier lifetime, forming a hot-phonon bottleneck. Furthermore, our study provides detailed insight into the exciton–phonon coupling and its role in carrier cooling in two-dimensional perovskites relevant for developing emerging hybrid semiconductor materials with tailored properties.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Nature of polariton transport in a Fabry-Perot cavity

Fabry-Perot microcavities can strongly enhance interactions between light and molecules, leading to the formation of hybrid light-matter states known as polaritons. Polaritons possess much smaller effective masses and much larger group velocities when the molecules are resonant with cavity modes that have finite (nonzero) in-plane wave vectors, giving rise to the possibilities of long-range and ultrafast ballistic transport. In this paper, we present the results of numerical simulations of the ultrafast ballistic transport phenomenon in real space and time during and after initialization with a short, spatially localized pulse. Here, we address this problem with two approaches: the standard transfer-matrix method (TMM) for planar structures and a second simulation based on the numerical solution of the Maxwell-Bloch equations that can be used for general configurations (complex metasurfaces, for instance) and excitation modes. The agreement between the TMM and the full numerical calculation with the Maxwell-Bloch equations when applied to multilayer planar configurations provides proof of the validity of both approaches for the present analyses. Overall, we find that the transport of the molecular excitons inside the cavity synchronize with the evolution of the enhanced electromagnetic field inside the cavity. Moreover, the synchronized transport rate is in good agreement with the group velocities predicted from a calculated dispersion relation across a wide range of frequencies. Finally, we relate the group velocity to the Hopfield coefficient obtained from quantum modeling and suggest that the dependence of light-matter coupling on the in-plane wave vector can be an important but overlooked factor for understanding the transport behavior of polaritons. These simulations provide an intuitive tool for understanding the collective motion of light and excitons and helps us to better understand how experimental observations of polaritons should be interpreted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Reward based optimization of resonance-enhanced piezoresponse spectroscopy

Dynamic spectroscopies in scanning probe microscopy (SPM) are critical for probing material properties, such as force interactions, mechanical properties, polarization switching, electrochemical reactions, and ionic dynamics. However, the practical implementation of these measurements is constrained by the need to balance imaging time and data quality. Signal to noise requirements favor long acquisition times and high frequencies to improve signal fidelity. However, these are limited on the low end by contact resonant frequency and photodiode sensitivity and on the high end by the time needed to acquire high-resolution spectra or the propensity for sample degradation under high field excitation over long times. The interdependence of key parameters such as instrument settings, acquisition times, and sampling rates makes manual tuning labor-intensive and highly dependent on user expertise, often yielding operator-dependent results. These limitations are prominent in techniques like dual amplitude resonance tracking in piezoresponse force microscopy that utilize multiple concurrent feedback loops for topography and resonance frequency tracking. Here, a reward-driven workflow is proposed that automates the tuning process, adapting experimental conditions in real time to optimize data quality. Furthermore, this approach significantly reduces the complexity and time required for manual adjustments and can be extended to other SPM spectroscopic methods, enhancing overall efficiency and reproducibility.

47 OTHER INSTRUMENTATION↗

DOE OSTI2025

An NV − center in magnesium oxide as a spin qubit for hybrid quantum technologies

Recent predictions suggest that oxides, such as MgO and CaO, could serve as hosts of spin defects with long coherence times and thus be promising materials for quantum applications. However, in most cases, specific defects have not yet been identified. Here, by using a high-throughput first-principles framework and advanced electronic structure methods, we identify a negatively charged complex between a nitrogen interstitial and a magnesium vacancy in MgO with favorable electronic and optical properties for hybrid quantum technologies. We show that this NV − center has stable triplet ground and excited states, with singlet shelving states enabling optical initialization and spin-dependent readout. We predict several properties, including absorption, emission, and zero-phonon line energies, as well as zero-field splitting tensor, and hyperfine interaction parameters, which can aid in the experimental identification of this defect. Our calculations show that due to a strong pseudo-Jahn Teller effect and low-frequency phonon modes, the NV − center in MgO is subject to a substantial vibronic coupling. We discuss design strategies to reduce such coupling and increase the Debye-Waller factor, including the effect of strain and the localization of the defect states. We propose that the favorable properties of the NV − defect, along with the technological maturity of MgO, could enable hybrid classical-quantum applications, such as spintronic quantum sensors and single qubit gates.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Real-Frequency Response Functions at Finite Temperature

Building on previous developments [A. Taheridehkordi, S. H. Curnoe, and J. P. F. LeBlanc, Phys. Rev. B 99, 035120 (2019); A. Taheridehkordi, S. H. Curnoe, and J. P. F. LeBlancPhys. Rev. B101, 125109 (2020); A. Taheridehkordi, S. H. Curnoe, and J. P. F. LeBlancPhys. Rev. B102, 045115 (2020), B. Holm and U. von Barth, Phys. Rev. B 57, 2108 (1998), J. Vičičevic and M. Ferrero, Phys. Rev. B 101, 075113 (2020)], we show that the diagrammatic Monte Carlo technique allows us to compute finite-temperature response functions directly on the real-frequency axis within any field-theoretical formulation of the interacting fermion problem. There are no limitations on the type and nature of the system’s action or whether partial summation and self-consistent treatment of certain diagram classes are used. In particular, by eliminating the need for numerical analytic continuation from a Matsubara representation, our scheme allows us to study spectral densities of arbitrary complexity with controlled accuracy in models with frequency-dependent effective interactions. Finally, for illustrative purposes we consider the problem of the plasmon linewidth in a homogeneous electron gas (jellium).

3-dimensional systems↗