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DOE OSTI2021

From Intermolecular Interaction Energies and Observable Shifts to Component Contributions and Back Again: A Tale of Variational Energy Decomposition Analysis

Quantum chemistry in the form of density functional theory (DFT) calculations is a powerful numerical experiment for predicting intermolecular interaction energies. However, no chemical insight is gained in this way beyond predictions of observables. Energy decomposition analysis (EDA) can quantitatively bridge this gap by providing values for the chemical drivers of the interactions, such as permanent electrostatics, Pauli repulsion, dispersion, and charge transfer. These energetic contributions are identified by performing DFT calculations with constraints that disable components of the interaction. This review describes the second-generation version of the absolutely localized molecular orbital EDA (ALMO-EDA-II). The effects of different physical contributions on changes in observables such as structure and vibrational frequencies upon complex formation are characterized via the adiabatic EDA. Example applications include red- versus blue-shifting hydrogen bonds; the bonding and frequency shifts of CO, N 2 , and BF bound to a [Ru(II)(NH 3 ) 5 ] 2 + moiety; and the nature of the strongly bound complexes between pyridine and the benzene and naphthalene radical cations. Additionally, the use of ALMO-EDA-II to benchmark and guide the development of advanced force fields for molecular simulation is illustrated with the recent, very promising, MB-UCB potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

Comment on “The Mössbauer rotor experiment and the general theory of relativity” [Ann. Physics 368 (2016) 258–266]

Highlights: •Our approach is considered from the viewpoint of arbitrary moving continuum. •Continuum characteristics are determined by a deformation tensor, a stress tensor, a strain velocity tensor, a spin tensor (Sing (1963)) and the first curvature vectors of the world lines of medium particles. •All these physical values are located on the hypersurfaces orthogonal to the world lines of medium particles and specify the “physical” space. •The time counting from the “physical” space permits to obtain the red shift of the frequency at the end of the tube that coincides with Corda result (Corda (2016)).

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2020

Design Optimization for Weighted Conduction Loss Minimization in a Dual-Active-Bridge-Based PV Microinverter

This manuscript presents a harmonic-superposition based frequency-domain approach for analysis and optimal design of a single-stage DAB-based DC-AC converter used in low-voltage DC to high voltage AC applications, such as PV microinverter. Specifically, two topological variations and correspondingly different modulation strategies involving up to four control variables (three phase shifts and switching frequency) are analyzed. Optimal trajectories of control variables are determined that result in minimized transformer RMS current at a given average power, while enforcing near-uniform ZVS. To make the design process holistic, an outer optimization loop is used to determine optimal values for the power transfer inductance (integrated as the transformer’s leakage inductance) and turns ratio, which minimize the weighted-average conduction loss contribution to the microinverter’s CEC efficiency. Based on the optimization analyses, a 400 W microinverter prototype is built and experimental results at one operating point are presented, achieving a measured efficiency of 92.8%.

14 SOLAR ENERGY↗

DOE OSTI2021

Phase-sensitive γ-encoded recoupling of heteronuclear dipolar interactions and 1 H chemical shift anisotropy

γ-encoded recoupling sequences are known to produce strong amplitude modulations that lead to sharp doublets when Fourier transformed. These doublets depend very little on the recoupled tensor asymmetry and thus enable for the straightforward determination of dynamic order parameters. It can, however, be difficult to measure small anisotropies, or small order parameters, using such sequences; the resonances from the doublet may overlap with each other, or with the zero-frequency glitch. This limitation has prevented the widespread use of 1 H chemical shift anisotropy (CSA) for the measurement of dynamics, particularly for CH protons which typically have CSAs of only a few ppm when immobile. In this work, we introduce a simple modification to the traditional 1 H CSA and proton-detected local field pulse sequences that enables the acquisition of a hypercomplex dataset and the removal of the uncorrelated magnetization that results in the zero-frequency glitch. These new sequences then yield a frequency shift in the indirect dimension, rather than a splitting, which is easily identifiable even in cases of weak interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Intramolecular Polarization Contributions to the pKa’s of Carboxylic Acids Through the Chain Length Dependence of Vibrational Tag-Shifts in Cryogenically Cooled Pyridinium-(CH2)n-COOH (n = 1-7) Cations

The pKa’s of acids are known to depend on the ionic strength of an electrolyte solution, an effect that qualitatively results from electrostatic interactions of the acid and conjugate base with proximal ions. Here we explore an intramolecular variation on this theme in which a carboxylic acid group is tethered to a pyridinium cationic charge center with increasingly long alkyl linkages in the series Py+-(CH2)n-COOH, with n = 1-7. The effective acidities of the carboxylic acid group in the isolated cations are determined by recording the red-shifts in the frequencies of the acid OH stretches upon attachment to D2 and N2 molecules, measured by using cryogenic ion spectroscopy. The short chains indeed lead to substantial increases in acidity, with the effect falling off in the range of n = 4-5. The response of the CO stretch on the acid head group is surprisingly strong and, in contrast to the expected red shift of the OH, displays a blue shift as the chain length is reduced. Electronic structure calculations recover these trends and indicate that the proximal cationic charge center acts to draw electron density away from the acid C=O bond. This acts to blue shift the CO stretch while weakening the C-C bond that attaches the head group to the chain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Strong parametric dispersive shifts in a statically decoupled two-qubit cavity QED system

Qubits in cavity quantum electrodynamic (QED) architectures are often operated in the dispersive regime, in which the operating frequency of the cavity depends on the energy state of the qubit, and vice versa. The ability to tune these dispersive shifts provides additional options for performing either quantum measurements or logical manipulations. Here we couple two transmon qubits to a lumped-element cavity through a shared superconducting quantum interference device (SQUID). In this work, our design balances the mutual capacitive and inductive circuit components so that both qubits are statically decoupled from the cavity with low flux sensitivity, offering protection from decoherence processes. Parametric driving of the SQUID flux enables independent, dynamical tuning of each qubit’s interaction with the cavity. As a practical demonstration, we perform pulsed parametric dispersive readout of both qubits. The dispersive frequency shifts of the cavity mode follow the theoretically expected magnitude and sign. This parametric approach creates an extensible, tunable cavity QED framework with various future applications, such as entanglement and error correction via multi-qubit parity readout, state and entanglement stabilization, and parametric logical gates.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2025

Can Charge Transfer Across C─H⋅⋅⋅O Hydrogen Bonds Stabilize Oil Droplets in Water?

Oil-water emulsions resist aggregation due to the presence of negative charges at their surface that leads to mutual repulsion between droplets, but the molecular origin of oil charge is currently under debate. Although much evidence has suggested that ionic species must accumulate at the interface, an alternative perspective attributes the negative charge on the oil droplet to charge transfer of electron density from water to oil molecules. Although the charge transfer mechanism is consistent with the correct sign of oil charge, it is just as important to provide good estimates of the charge magnitude to explain emulsion stability and electrophoresis experiments. Here, we show using energy decomposition analysis that the amount of net flow of charge from water to oil is negligibly small due to nearly equal forward and backward charge transfer through weak oil-water interactions, such that oil droplets would be unstable and coalesce, contrary to experiment. The lack of charge transfer also explains why vibrational sum frequency scattering reports a blue shift in the oil C-H frequency when forming emulsions with water, which arises from Pauli repulsion due to localized confinement at the interface. Finally, unlike ions, neither charge transfer nor dynamic polarization can produce a finite conductivity needed to couple to electric fields that would explain electrophoretic mobility.

Zhao, Ruoqi↗

DOE OSTI2020

Optimum power analysis of a self-reactive wave energy point absorber with mechanically-driven power take-offs

This paper studies a self-reactive ocean wave energy converter (WEC) where energy is absorbed through the relative motion between a floating buoy on the ocean surface and a submerged body. Two types of direct-drive power take off (PTO) systems are examined. One adopts a ball screw system in inverse driving mode with mechanical motion rectifier (MMR) that converts the oscillating bi-directional input heave motion into unidirectional rotation to drive an electromagnetic generator, and another one uses a ball screw system to directly drive the generator (called non-MMR). Dynamic models for both types of PTOs are established and integrated with the overall WEC system model in both the time and frequency domains. Numerical simulation is used to investigate the dynamic performance of both PTOs. The influences of the PTO inerter, which is from the rotational inertia of the flywheel and generator, and the WEC drag damping coefficient are discussed and explored. The analytical closed-form solution for the optimum condition of the non-MMR system is derived based on the criterion of maximum power absorption, and numerical simulation yields the optimum condition for the MMR system. Overall, the results under regular and irregular waves show that the PTO inerter in the MMR system can improve the power absorption for small wave periods and maintain the same performance for large wave periods. The PTO inerter in the non-MMR system shifts the peak frequency. The WEC drag damping negatively influences the power absorption in both PTO systems, especially at large wave periods.

16 TIDAL AND WAVE POWER↗

DOE OSTI2023

River Geomorphology Affects Biogeochemical Responses to Hydrologic Events in a Large River Ecosystem

Shifts in the frequency and intensity of high discharge events due to climate change may have important consequences for the hydrology and biogeochemistry of rivers. However, our understanding of event-scale biogeochemical dynamics in large rivers lags that of small streams. To fill this gap, we used high-frequency sensor data collected during four consecutive summers from a main channel and backwater site of the Upper Mississippi River. We identified high discharge events and calculated event concentration-discharge responses for both physical-chemical (nitrate, turbidity, and fluorescent dissolved organic matter) and biological (chlorophyll-a and cyanobacteria) constituents using metrics of hysteresis and slope. We found a range of responses across events, particularly for nitrate. Although fluorescent dissolved organic matter (FDOM) and turbidity exhibited more consistent responses across events, contrasting hysteresis metrics indicated that FDOM was flushed to the river from more distant sources than turbidity. Biological responses (chlorophyll a and cyanobacteria) differed more between sites than physical and chemical constituents. Lastly, we found that the event characteristics best explaining concentration responses differed between sites, with event magnitude more frequently related to responses in the main channel, and antecedent wetness conditions associated with response variation in the backwater. Furthermore, our results indicate that event responses in large rivers are distinct across the diverse habitats and biogeochemical components of a large floodplain river, which has implications for local and downstream ecosystems as the climate shifts.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Syntheses and Crystal Structures of Rare-Earth Oxyapatites Ca 2 RE 8 (SiO 4 ) 6 O 2 (RE = Pr, Tb, Ho, Tm)

Four different rare-earth oxyapatites of Ca 2 RE 8 (SiO 4 ) 6 O 2 (RE = Pr, Tb, Ho, Tm) were synthesized using a solution-based method followed by drying, calcination, and high-temperature sintering in air. X-ray powder diffraction and Raman spectroscopy were performed on the synthesized oxyapatites. Here, the RE oxyapatites crystallize in the hexagonal space group P6 3 /m with similar unit cell parameters, increasing linearly with larger RE cations. The unit cell volumes increase linearly whereas the densities decrease nonlinearly with larger RE cations. Raman spectra showed intense bands of the symmetric bending and stretching modes of SiO 4 at ~ 400 and 860 cm -1 regions, respectively. The bands generally shifted to higher frequencies with smaller RE cations in the structures.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Microcystin-LR aerosol induces inflammatory responses in healthy human primary airway epithelium

Harmful algal blooms plague bodies of freshwater globally. These blooms are often composed of outgrowths of cyanobacteria capable of producing the heptapeptide Microcystin-LR (MC-LR) which is a well-known hepatotoxin. Recently, MC-LR has been detected in aerosols generated from lake water. However, the risk for human health effects due to MC-LR inhalation exposure have not been extensively investigated. In this study, we exposed a fully differentiated 3D human airway epithelium derived from 14 healthy donors to MC-LR-containing aerosol for 3 minutes per day for 3 days. Concentrations of MC-LR ranged from 100 pM to 1 µM. Although there were little to no detrimental alterations in measures of the airway epithelial function (i.e. cell survival, tissue integrity, mucociliary clearance, or cilia beating frequency), a distinct shift in the transcriptional activity was found. Genes related to inflammation were found to be upregulated such as C-C motif chemokine 5 (CCL5; log2FC = 0.56 , p = 0.02) and C-C chemokine receptor type 7 (CCR7; log2FC = 0.83, p = 0.03). Functionally, conditioned media from MC-LR exposed airway epithelium was also found to have significant chemo-attractive properties for primary human neutrophils. Additionally, increases were found in the concentration of secreted chemokine proteins in the conditioned media such as CCL1 (log2FC = 5.07 , p = 0.0001) and CCL5 (log2FC = 1.02, p = 0.046). These results suggest that MC-LR exposure to the human airway epithelium is capable of inducing an inflammatory response that may potentiate acute or chronic disease.

3D human airway epithelium↗

DOE OSTI2022

Performance of multifunctional piezoelectric energy harvesting microgyroscopes with material degradation

Most microelectromechanical systems (MEMS) are made from brittle materials that are prone to cracking. Damage from the formation of cracks can occur anytime during the manufacturing process or due to mechanical loading of MEMS devices. Cracks can increase the structures flexibility and lead to changes in performance or total failure. Understanding the potential influences cracks in MEMS is necessary for the longevity of these systems. The energy harvesting microgyroscope studied in this work is susceptible to crack propagation in its silicon substrate and lead zirconate titanate piezoelectric patch. To this end, an electromechanical model is developed to capture the impacts of cracks on the performance of a damaged energy harvesting microgyroscope. Numerical methods are used to approximate the damage associated with distributed crack networks. Then, the static and dynamic responses of the damaged microgyroscope are analyzed for two possible multifunctional setups. Here, the current study revealed that cracks can significantly affect the static and dynamic behaviors of the microgyroscope energy harvester. Combinations of cracking and piezoelectric property degradation cause a decrease in the static pull-in voltage and shift the resonance frequencies of the system. Additionally, it is shown that the systems sensitivity to changes in the base rotation and energy harvesting capabilities vary widely depending on the severity of material degradation.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Ballistic-diffusive phonon transport in cellulose nanocrystals by ReaxFF molecular dynamics simulations

Cellulose nanocrystals (CNCs), a ubiquitous nano-sized natural biopolymer, have drawn considerable attention in recent years due to their excellent mechanical and chemical properties. However, thermal properties of CNCs, which are critical for their potential applications as structural or functional materials, are less investigated. In this work, their thermal properties were systematically studied by molecular dynamics (MD) simulations in terms of the effects of polymorphs, size, temperature, and strain. It was found that the thermal conductivities depend on the polymorphs of CNCs, but the thermal conductance of unit chain of each polymorph is similar. Moreover, the strong dependence of the thermal conductivities of CNCs on their length and cross-sectional area indicates the existence of remarkable ballistic-diffusive phonon transport. Single chain CNCs can achieve a thermal conductivity of ~6 W/(m∙K), implying their potential as high thermal conductive polymer. The mechanical strain can enhance the alignment of cellulose skeleton, which reduces phonon scattering and thus increases thermal conductivity. Possible underlying mechanism of the varying thermal conductivity was further discussed and attributed to the shift of phonon frequencies and varied degree of orientation. This study reveals the sophisticated ballistic-diffusive phonon transport in CNCs, and pave path to future design of CNC-based materials with desirable thermal properties.

42 ENGINEERING↗

DOE OSTI2021

A mechanistic understanding of oxygen isotopic changes in the Western United States at the Last Glacial Maximum

At the Last Glacial Maximum (LGM), records suggest drier conditions in the northwest United States and wetter conditions in the southwest United States relative to present-day as well as widespread changes in the isotopic composition of water. However, the mechanisms responsible for these changes remain ambiguous. Here, we explore differences in western United States hydroclimate between the LGM and preindustrial with a water isotope tracer enabled Earth System Model. We then use proxy forward models to compare simulated and recorded δ 18 O in speleothems. We find that the pattern of hydroclimate response in the western United States at the LGM relates to a combination of 1) increased frequency and southward shifted wintertime extratropical cyclones in the North Pacific, 2) greater rainout of moisture as it moves over the continent, and 3) reduced evaporation in the cooler LGM climate. The simulated lower δ 18 O of precipitation at the LGM relates predominantly to an increase in cool season moisture removal efficiency, with a secondary contribution from relatively more cool season precipitation. Both surface temperatures and North American ice sheets contribute to these hydroclimate changes at the LGM. Comparisons between δ 18 O from proxy forward models and speleothem records in the western United States show general agreement at the LGM, with increasing depletion moving towards the continental interior. Finally, this study highlights the similarities and differences between hydrologic and δ 18 O changes at the LGM and emphasizes the utility of model-proxy comparison for interpretation.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Characterization and interaction of geometric and contact/impact nonlinearities in dynamical systems

Here, we study how a contact/impact nonlinearity interacts with a geometric cubic nonlinearity in an oscillator system. Specific focus is shown to the effects on bifurcation behavior and secondary resonances (i.e., super- and sub-harmonic resonances). The effects of the individual nonlinearities are first explored for comparison, and then the influences of the combined nonlinearities, varying one parameter at a time, are analyzed and discussed. Nonlinear characterization is then performed on an arbitrary system configuration to study super- and sub-harmonic resonances and grazing contacts or bifurcations. Both the cubic and contact nonlinearities cause a drop in amplitude and shift up in frequency for the primary resonance, and they activate high-amplitude subharmonic resonance regions. The nonlinearities seem to never destructively interfere. The contact nonlinearity generally affects the system’s superharmonic resonance behavior more, particularly with regard to the occurrence of grazing contacts and the activation of many bifurcations in the system’s response. The subharmonic resonance behavior is more strongly affected by the cubic nonlinearity and is prone to multistable behavior. Perturbation theory proved useful for determining when the cubic nonlinearity would be dominant compared to the contact nonlinearity. The limiting behaviors of the contact stiffness and freeplay gap size indicate the cubic nonlinearity is dominant overall. It is demonstrated that the presence of contact may result in the activation of several bifurcations. In addition, it is proved that the system’s subharmonic resonance region is prone to multistable dynamical responses having distinct magnitudes.

42 ENGINEERING↗

DOE OSTI2024

Seasonal Controls on Microbial Depolymerization and Oxidation of Organic Matter in Floodplain Soils

Floodplain soils are vast reservoirs of organic carbon often attributed to anaerobic conditions that impose metabolic constraints on organic matter degradation. What remains elusive is how such metabolic constraints respond to dynamic flooding and drainage cycles characteristic of floodplain soils. Here, in this work, we show that microbial depolymerization and respiration of organic compounds, two rate-limiting steps in decomposition, vary spatially and temporally with seasonal flooding of mountainous floodplain soils (Gothic, Colorado, USA). Combining metabolomics and -proteomics, we found a lower abundance of oxidative enzymes during flooding coincided with the accumulation of aromatic, high-molecular weight compounds, particularly in surface soils. In subsurface soils, we found that a lower oxidation state of carbon coincided with a greater abundance of chemically reduced, energetically less favorable low-molecular weight metabolites, irrespective of flooding condition. Our results suggest that seasonal flooding temporarily constrains oxidative depolymerization of larger, potentially plant-derived compounds in surface soils; in contrast, energetic constraints on microbial respiration persist in more reducing subsurface soils regardless of flooding. Our work underscores that the potential vulnerability of these distinct anaerobic carbon storage mechanisms to changing flooding dynamics should be considered, particularly as climate change shifts both the frequency and extent of flooding in floodplains globally.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Ion specific, thin film confinement effects on conductivity in polymerized ionic liquids.

Acrylate-based polymerized ionic liquids (PILs) with ammonium (Am) or imidazolium (Im) cations and tetrafluoroborate (BF4) or bis(trifluoromethanesulfonyl)imide (TFSI) anions were synthesized and spin coated onto gold interdigitated electrodes on silica to investigate nanoconfinement effects on ion transport. The film thickness ranged from 23 to 313 nm. A significant reduction of the in-plane conductivity was observed in some PIL thin films with thickness below 100 nm. Specifically, Am BF4 PIL showed the largest conductivity drop (ca. 50% difference between a 22 nm and a 261 nm film) while Im TFSI PIL showed almost no change under confinement. The difference in conductivity drop is discussed in terms of (i) differences in interfacial layer thickness by fitting a two-layer conductivity model and (ii) potential changes in glass transition temperature (T-g) under confinement, which were estimated using the Vogel-Fulcher-Tammann fits of bulk conductivities. Decreasing film thickness also caused the dielectric loss peaks to shift to lower frequency, indicating that the ion diffusion process slowed under confinement.

Zhao, Qiujie↗

DOE OSTI2022

Reconfigurable quantum phononic circuits via piezo-acoustomechanical interactions

Abstract We show that piezoelectric strain actuation of acoustomechanical interactions can produce large phase velocity changes in an existing quantum phononic platform: aluminum nitride on suspended silicon. Using finite element analysis, we demonstrate a piezo-acoustomechanical phase shifter waveguide capable of producing ± π phase shifts for GHz frequency phonons in 10s of μm with 10s of volts applied. Then, using the phase shifter as a building block, we demonstrate several phononic integrated circuit elements useful for quantum information processing. In particular, we show how to construct programmable multi-mode interferometers for linear phononic processing and a dynamically reconfigurable phononic memory that can switch between an ultra-long-lifetime state and a state strongly coupled to its bus waveguide. From the master equation for the full open quantum system of the reconfigurable phononic memory, we show that it is possible to perform read and write operations with over 90% quantum state transfer fidelity for an exponentially decaying pulse.

Taylor, Jeffrey C. (ORCID:0000000215982436)↗