Orientations of nonlocal vibrational modes from combined experimental and theoretical sum frequency spectroscopy
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Chase, Hilary M.↗
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Economic dispatch for electricity merchant with energy storage and wind plant: State of charge based decision making considering market impact and uncertainties
Here this paper investigates how the market impact of electricity merchants and uncertainty of wind generation affect their co-optimized scheduling policy, specifically for merchants who have both energy storage and wind plants. In the existing literature, merchants' trading actions are usually assumed not to affect market prices; however, a large-scale energy storage merchant's actions can affect market prices. To this end, we approximate the electricity price by a linear function of the quantity of power traded by the merchant in the reward function to achieve decision-making incorporating the market impact. This paper utilizes the dynamic programming approach to analyze merchants' optimal multi-period decision-making incorporating market impact, uncertain wind generation, and energy storage constraints. First, our results demonstrate that for a merchant with co-located energy storage facilities and wind power plants, the energy storage's feasible state of charge (SOC) range can be segmented into four possible sub-ranges by three analytically developed SOC reference points. The unique optimal trading decision can be achieved by comparing the current energy inventory and the SOC references of the next period. Second, our results show that market impact and uncertainties substantially change the optimal storage scheduling policy by impacting the values of the reference points. To mitigate the negative effect of the merchant's market impact on buying and selling actions, the merchant may reduce the amount of generating or pumping electricity each period to maximize profit. Moreover, we identify and investigate the trade-off between market price and transaction quantity. Our findings provide co-optimized scheduling guidance for electricity merchants with co-located energy storage and renewable power plants systems.
17 WIND ENERGY↗
Evolution of Strain in Heteroepitaxial Cadmium Carbonate Overgrowths on Dolomite
The evolution and accommodation of lattice strain in an epitaxial mineral film grown on an isostructural substrate were observed as a function of film thickness. Cadmium carbonate films (approximately CdCO 3 (otavite) in composition) were grown on the (104) surface of CaMg(CO 3 ) 2 (dolomite) from aqueous solutions that were supersaturated with respect to both pure otavite and Cd-rich (Cd 1-x Ca x )CO 3 . Specular and non-specular X-ray reflectivity (XR) revealed that the structure and strain of the otavite overgrowths evolved in a manner that is fully consistent with a Stranski-Krastanov growth mode. Otavite films initially grew as coherently strained films, up to an average thickness of ~15 Å, with lateral compressive strains and an expansion of the vertical film lattice spacing resulting in a unit cell volume consistent with pure otavite. Thicker films (>15 Å) became incommensurate with the substrate, having lattice parameters that are indistinguishable from pure otavite. These results indicate that the evolution of these mineral films is controlled by epitaxy and are consistent with the growth of essentially pure otavite films. Lastly, these results provide a foundation for understanding the stability of thin-film overgrowths in the natural environment.
36 MATERIALS SCIENCE↗
Integrated Quantum-Classical Protocol for the Realistic Description of Solvated Multinuclear Mixed-Valence Transition-Metal Complexes and Their Solvatochromic Properties
Linear cyanide-bridged polymetallic complexes, which undergo photoinduced metal-to-metal charge transfer, represent prototypical systems for studying long-range electron-transfer reactions and understanding the role played by specific solute–solvent interactions in modulating the excited-state dynamics. Here, to tackle this problem, while achieving a statistically meaningful description of the solvent and of its relaxation, one needs a computational approach capable of handling large polynuclear transition-metal complexes, both in their ground and excited states, as well as the ability to follow their dynamics in several environments up to nanosecond time scales. Here, we present a mixed quantum classical approach, which combines large-scale molecular dynamics (MD) simulations based on an accurate quantum mechanically derived force field (QMD-FF) and self-consistent QMD polarized point charges, with IR and UV–vis spectral calculations to model the solvation dynamics and optical properties of a cyano-bridged trinuclear mixed-valence compound (trans-[(NC) 5 Fe III (μ-CN)Ru II (pyridine) 4 (μ-NC)Fe III (CN) 5 ] 4– ). We demonstrate the reliability of the QMD-FF/MD approach in sampling the solute conformational space and capturing the local solute–solvent interactions by comparing the results with higher-level quantum mechanics/molecular mechanics (QM/MM) MD reference data. The IR spectra calculated along the classical MD trajectories in different solvents correctly predict the red shift of the CN stretching band in the aprotic medium (acetonitrile) and the subtle differences measured in water and methanol, respectively. By explicitly including the solvent molecules around the cyanide ligands and calculating the thermal averaged absorption spectra using time-dependent density functional theory calculations within the Tamm–Dancoff approximation, the experimental solvatochromic shift is quantitatively reproduced going from water to methanol, while it is overestimated for acetonitrile. This discrepancy can likely be traced back to the lack of important dispersion interactions between the solvent cyano groups and the pyridine substituents in our micro solvation model. The proposed protocol is applied to the ground state in water, methanol, and acetonitrile and can be flexibly generalized to study excited-state nonequilibrium solvation dynamics.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Norm-conserving pseudopotentials and basis sets to explore Lanthanide chemistry in complex environments
A complete set of pseudopotentials and accompanying basis sets for all lanthanide elements are presented based on the relativistic, norm-conserving, separable, dual-space Gaussian-type pseudopotential protocol of Goedecker, Teter and Hutter (GTH) within the generalized gradient approximation (GGA) and the exchange-correlation functional of Perdew, Burke and Ernzerhof (PBE). The corresponding basis sets have been molecularly optimized (MOLOPT) using a contracted form with a single set of Gaussian exponents for s, p and d states. The f states are uncontracted explicitly with Gaussian exponents. Moreover, the Hubbard U values for each lanthanide element, to be used in DFT+U calculations, are also tabulated, allowing for the proper treatment of the strong on-site Coulomb interactions of localized 4f electrons. The accuracy and reliability of our GTH pseudopotentials and companion basis sets optimized for lanthanides is illustrated by a series of test calculations on lanthanide-centered molecules, and solid-state systems, with the most common oxidation states. We anticipate that these pseudopotentials and basis sets will enable larger-scale density functional theory calculations and ab initio molecular dynamics simulations of lanthanide molecules in either gas or condensed phases, as well as of solid state lanthanide-containing materials, allowing to further explore the chemical and physical properties of lanthanide systems.
Lu, Jun-Bo↗
Unraveling Excitonic Effects for the First Hyperpolarizabilities of Chromophore Aggregates
Excitonic interactions often significantly affect the optoelectronic properties of molecular materials. However, their role in determining the nonlinear optical response of organic electro-optic materials remains poorly understood. In this paper, we explore the effects of excitonic interactions on the first hyperpolarizability for aggregates of donor–acceptor chromophores. We show that calculations of the first hyperpolarizabilty of chromophore aggregates based on a two-state model agree well with the more rigorous coupled perturbed Hartree–Fock method. We then use both time-dependent density functional theory calculations and the molecular exciton approximation to parametrize the two-state model. Use of the molecular exciton approximation to the two-state model (i) is appropriate for disordered aggregates (unlike band theory), (ii) is computationally efficient enough for calculating the first hyperpolarizability of materials that consist of thousands of interacting chromophores, and (iii) allows the unraveling of the effects of both excitonic interactions and electrostatic polarization of the chromophore electron density by its environment on the first hyperpolarizability of molecular materials. We find that use of the molecular exciton approximation to the two-state model does not introduce significant additional errors compared to those introduced by applying the two-state model alone. We determine that the absolute change to the first hyperpolarizability of chromophore aggregates due to excitonic interactions increases with the size of the aggregate. For all sizes of disordered aggregates of chromophores considered in this paper, the inclusion of excitonic interactions on average decreases the magnitude of the first hyperpolarizability by 12–14% compared to the case of non-interacting chromophores. Lastly, we present a method for analytically calculating the first hyperpolarizability of a one-dimensional periodic array of chromophores within the molecular exciton approximation to the two-state model. This technique can be used to include an approximate correction for excitonic effects when simulating the electro-optic response of disordered and ordered organic materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Facile Electron Transfer to CO 2 during Adsorption at the Metal|Solution Interface
We estimate the rate of electron transfer to CO 2 at the Au (211)|water interface during adsorption in an electrochemical environment under reducing potentials. On the basis of density functional theory calculations at the generalized gradient approximation and hybrid levels of theory, we find electron transfer to the adsorbed *CO 2 to be very facile. This high rate of transfer is estimated by the energy distribution of the adsorbate-induced density of states as well as from the interaction between diabatic states representing neutral and negatively charged CO 2 . Up to 0.62 electrons is transferred to CO 2 , and this charge adiabatically increases with the bending angle to a lower limit of 137°. Finally, we conclude that this rate of electron transfer is extremely fast compared to the time scale of the nuclear degrees of freedom, that is, the adsorption process.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Regioselective On-Surface Synthesis of [3]Triangulene Graphene Nanoribbons
The integration of low-energy states into bottom-up engineered graphene nanoribbons (GNRs) is a robust strategy for realizing materials with tailored electronic band structure for nanoelectronics. Low-energy zero-modes (ZMs) can be introduced into nanographenes (NGs) by creating an imbalance between the two sublattices of graphene. This phenomenon is exemplified by the family of [n]triangulenes (n ϵ $\mathbb{N}$). Here, we demonstrate the synthesis of [3]triangulene-GNRs, a regioregular one-dimensional (1D) chain of [3]triangulenes linked by five-membered rings. Hybridization between ZMs on adjacent [3]triangulenes leads to the emergence of a narrow band gap, E g,exp ~ 0.7 eV, and topological end states that are experimentally verified using scanning tunneling spectroscopy. Tight-binding and first-principles density functional theory calculations within the local density approximation corroborate our experimental observations. Our synthetic design takes advantage of a selective on-surface head-to-tail coupling of monomer building blocks enabling the regioselective synthesis of [3]triangulene-GNRs. Detailed ab initio theory provides insights into the mechanism of on-surface radical polymerization, revealing the pivotal role of Au-C bond formation/breakage in driving selectivity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Volume Flow Rate Estimation for Small Explosions at Mt. Etna, Italy, From Acoustic Waveform Inversion
Rapid assessment of the volume and the rate at which gas and pyroclasts are injected into the atmosphere during volcanic explosions is key to effective eruption hazard mitigation. Here, we use data from a dense infrasound network deployed in 2017 on Mt. Etna, Italy, to estimate eruptive volume flow rates (VFRs) during small gas-and-ash explosions. We use a finite-difference time-domain approximation to compute the acoustic Green's functions and perform a full waveform inversion for a multipole source, combining monopole and horizontal dipole terms. The inversion produces realistic estimates of VFR, on the order of 4 × 10 4 m 3 /s and well-defined patterns of source directivity. This is the first application of acoustic waveform inversion at Mt. Etna. Our results demonstrate that acoustic waveform inversion is a mature and robust tool for assessment of source parameters and holds potential as a tool to provide rapid estimates of VFR in near real time.
58 GEOSCIENCES↗
Machine-learning guided search for phonon-mediated superconductivity in boron and carbon compounds
We present a workflow that iteratively combines ab-initio calculations with a machine-learning (ML) guided search for superconducting compounds with both dynamical stability and instability from imaginary phonon modes, the latter of which have been largely overlooked in previous studies. Electron-phonon coupling (EPC) properties and critical temperature (T c ) of 417 boron, carbon, and borocarbide compounds have been calculated with density functional perturbation theory (DFPT) and isotropic Eliashberg approximation. Our study addresses T c convergence of Brillouin zone sampling with an ansatz test, stabilizing imaginary phonon modes for significant EPC contributions, and comparing the performance of two ML models, especially when including compounds of dynamical instability. We predict a few promising superconducting compounds with formation energy just above the ground state convex hull, such as Ca 5 B 3 N 6 (35 K), TaNbC 2 (28.4 K), Nb 3 B 3 C (16.4 K), Y 2 B 3 C 2 (4.0 K), Pd 3 CaB (7.0 K), MoRuB 2 (15.6 K), RuVB 2 (15.0 K), RuSc 3 C 4 (6.6 K) among others.
Nepal, Niraj K. [Ames Laboratory (AMES), Ames, IA ↗
Microscopic origin of Cooper pairing in the iron-based superconductor Ba 1-x K x Fe 2 As 2
Resolving the microscopic pairing mechanism and its experimental identification in unconventional superconductors is among the most vexing problems of contemporary condensed matter physics. We show that Raman spectroscopy provides an avenue towards this aim by probing the structure of the pairing interaction at play in an unconventional superconductor. As we study the spectra of the prototypical Fe-based superconductor Ba 1-x K x Fe 2 As 2 for 0.22 ≤ x ≤ 0.70 in all symmetry channels, Raman spectroscopy allows us to distill the leading s-wave state. In addition, the spectra collected in the B1g symmetry channel reveal the existence of two collective modes which are indicative of the presence of two competing, yet sub-dominant, pairing tendencies of d x 2 -y 2 symmetry type. A comprehensive functional Renormalization Group and random-phase approximation study on this compound confirms the presence of the two sub-leading channels, and consistently matches the experimental doping dependence of the related modes. In conclusion, the consistency between the experimental observations and the theoretical modeling suggests that spin fluctuations play a significant role in superconducting pairing.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Cascade of transitions in twisted and non-twisted graphene layers within the van Hove scenario
Abstract Motivated by measurements of compressibility and STM spectra in twisted bilayer graphene, we analyze the pattern of symmetry breaking for itinerant fermions near a van Hove singularity. Making use of an approximate SU(4) symmetry of the Landau functional, we show that the structure of the spin/isospin order parameter changes with increasing filling via a cascade of transitions. We compute the feedback from different spin/isospin orders on fermions and argue that each order splits the initially 4-fold degenerate van Hove peak in a particular fashion, consistent with the STM data and compressibility measurements, providing a unified interpretation of the cascade of transitions in twisted bilayer graphene. Our results follow from a generic analysis of an SU(4)-symmetric Landau functional and are valid beyond a specific underlying fermionic model. We argue that an analogous van Hove scenario explains the cascade of phase transitions in non-twisted Bernal bilayer and rhombohedral trilayer graphene.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Toxoplasma gondii Manipulates Expression of Host Long Noncoding RNA during Intracellular Infection
Long noncoding RNA (lncRNA) are non-protein-coding transcripts greater than 200 nucleotides that regulate gene expression. The field of transcriptomics is only beginning to understand the role of lncRNA in host defense. Little is known about the role of lncRNA in the response to infection by intracellular pathogens such as Toxoplasma gondii. Using a microarray, we examined the differential expression of 35,923 lncRNAs and 24,881 mRNAs in mouse bone-marrow-derived macrophages during infection with high- and low-virulence T. gondii strains. We found that 1,522 lncRNA molecules were differentially regulated during infection with the high-virulence Type I strain, versus 528 with the less-virulent Type II strain. Of these lncRNAs, 282 were co-regulated with a nearby or overlapping mRNA–including approximately 60 mRNAs with immune-related functions. We validated the microarray for 4 lncRNAs and 4 mRNAs using qRT-PCR. Using deletion strains of T. gondii, we found that the secretory kinase ROP16 controls upregulation of lncRNAs Csf1-lnc and Socs2-lnc, demonstrating that the parasite directly manipulates host lncRNA expression. Given the number of regulated lncRNAs and the magnitude of the expression changes, we hypothesize that these molecules constitute both an additional regulatory layer in the host response to infection and a target for manipulation by T. gondii.
59 BASIC BIOLOGICAL SCIENCES↗
Thin-film GaN Schottky diodes formed by epitaxial lift-off
The performance of thin-film GaN Schottky diodes fabricated using a large-area epitaxial lift-off (ELO) process is reported in this work. Comparison of the device characteristics before and after lift-off processing reveals that the Schottky barrier height remains unchanged by the liftoff processing and is consistent with expectations based on metal-semiconductor work function differences, with a barrier height of approximately 1 eV obtained for Ni/Au contacts on n− GaN. However, the leakage current in both reverse and low-forward-bias regimes is found to improve significantly after ELO processing. Likewise, the ideality factor of the Schottky diodes also improves after ELO processing, decreasing from n = 1.12–1.18 before ELO to n = 1.04–1.10 after ELO. A possible explanation for the performance improvement obtained for Schottky diodes after substrate removal by ELO processing is the elimination of leakage paths consisting of vertical leakage along threading dislocations coupled with lateral conduction through the underlying n+ buffer layer that is removed in the ELO process. Epitaxial liftoff with GaN may enable significant improvement in device performance and economics for GaN-based electronics and optoelectronics.
Wang, Jingshan↗
Photoionization of the iodine 3d, 4s, and 4p orbitals in methyl iodide
Ionization of the I 3d, 4s, and 4p orbitals in methyl iodide (CH 3 I) has been studied by using synchrotron radiation to measure the total ion yield and by recording photoelectron spectra with linearly polarized radiation in two polarization orientations. The complete photoelectron spectrum of CH 3 I has been recorded at several photon energies, and bands due to the C 1s, I 3d, 4s, 4p, and 4d atomic-like orbitals, as well as the molecular orbitals, have been observed and assigned. In the vicinity of the I 3d 5/2 and 3d 3/2 ionization thresholds at 626.8 and 638.3 eV, respectively, the ion yield displays weak structure in the pre-edge region due to transitions into valence or Rydberg states, and, at higher energies, a shoulder and a broad maximum attributed to the I 3d 5/2 → εf and the I 3d 3/2 → εf shape resonances, respectively. The absorption spectrum calculated using time-dependent density functional theory, within the Tamm-Dancoff approximation, has allowed assignments to be proposed for the valence and Rydberg states. The Stieltjes imaging technique has been used to simulate the absorption spectrum above the ionization threshold and indicates that transitions into the f(l = 3) continuum channel dominate. This conclusion has been corroborated by a Continuum Multiple Scattering–Xα (CMS–Xα) calculation. The asymmetric broadening of the photoelectron bands associated with the I 3d orbital, due to post collision interaction, is taken into account in our experimental analysis. Experimentally derived photoelectron anisotropy parameters for the I 3d orbital are in good agreement with the theoretical predictions obtained with the CMS–Xα approach. The I 3d shake-up/shake-off photoelectron spectrum has been recorded, and assignments have been proposed for several of the satellites. The M 4 N 45 N 45 and M 5 N 45 N 45 Auger electron yields have been measured, and that for the M 5 N 45 N 45 decay exhibits a maximum due to interchannel coupling between the 3d5/2 and 3d3/2 continua. The photoelectron band associated with the I 4p orbital has an unusual appearance. Based upon previous theoretical work for the analogous Xe 4p orbital, it appears that the initial I 4p -1 hole state decays rapidly through Coster-Kronig and super-Coster-Kronig transitions. This leads to a redistribution of the spectral intensity associated with the I 4p orbital and results in a photoelectron spectrum containing a single structured band together with an extended continuum. Another continuum is observed on the high binding energy side of the peak due to the 4s orbital, and we assign this to super-Coster-Kronig transitions into the 4p -1 4d -1 continuum.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Low energy peripheral scaling in nucleon–nucleon scattering and uncertainty quantification
We analyze the peripheral structure of the nucleon–nucleon interaction for LAB energies below 350 MeV. To this end we transform the scattering matrix into the impact parameter representation by analyzing the scaled phase shifts (L + 1/2) δ JLS (p) and the scaled mixing parameters (L + 1/2)ϵ JLS (p) in terms of the impact parameter b = (L + 1/2)/p. According to the eikonal approximation, at large angular momentum L these functions should become an universal function of b, independent on L. This allows to discuss in a rather transparent way the role of statistical and systematic uncertainties in the different long range components of the two-body potential. Implications for peripheral waves obtained in chiral perturbation theory interactions to fifth order (N5LO) or from the large body of NN data considered in the SAID partial wave analysis are also drawn from comparing them with other phenomenological high-quality interactions, constructed to fit scattering data as well. Here, we find that both N5LO and SAID peripheral waves disagree more than 5σ with the Granada-2013 statistical analysis, more than 2σ with the 6 statistically equivalent potentials fitting the Granada-2013 database and about 1σ with the historical set of 13 high-quality potentials developed since the 1993 Nijmegen analysis.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
A test of gravity with Pulsar Timing Arrays
Abstract A successful measurement of the Stochastic Gravitational Wave Background (SGWB) in Pulsar Timing Arrays (PTAs) would open up a new window through which to test the predictions of General Relativity (GR). We consider how these measurements might reveal deviations from GR by studying the overlap reduction function — the quantity that in GR is approximated by the Hellings-Downs curve — in some sample modifications of gravity, focusing on the generic prediction of a modified dispersion relation for gravitational waves. We find a distinct signature of such modifications to GR — a shift in the minimum angle of the angular distribution — and demonstrate that this shift is quantitatively sensitive to any change in the phase velocity. In a given modification of gravity, this result can be used, in some regions of parameter space, to distinguish the effect of a modified dispersion relation from that due to the presence of extra polarization modes.
Astronomy & Astrophysics↗
Scale matters
The applicability of Navier–Stokes equations is limited to near-equilibrium flows in which the gradients of density, velocity and energy are small. Here I propose an extension of the Chapman–Enskog approximation in which the velocity probability distribution function (PDF) is averaged in the coordinate phase space as well as the velocity phase space. I derive a PDF that depends on the gradients and represents a first-order generalization of local thermodynamic equilibrium. I then integrate this PDF to derive a hydrodynamic model. Finally, I discuss the properties of that model and its relation to the discrete equations of computational fluid dynamics.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗