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Results for “INTERMEDIATE COUPLING”
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Alkali Metal Control of Triplet-Mediated C–H Activation in Iron-Mediated Coupling of Dinitrogen and Benzene
Direct coupling of N 2 with abundant feedstocks like benzene to form N-containing organic compounds is a promising strategy for N 2 fixation pathways. The challenge of coupling N 2 activation and C–H bond oxidative addition was recently solved by introducing a reversible benzene C–H bond activation process mediated by a low-valent Fe(0) complex, which gave an organometallic product that could couple with partially reduced N 2 . Interestingly, the energetics of the C–H oxidative addition/reductive elimination step depends on the choice of alkali metal. However, the reason why the alkali metal influences the C–H bond activation remained elusive. In this work, we present a comprehensive study on this Fe(0)-mediated reversible C–H activation. Through density functional theory combined with high-level coupled cluster calculations, we discovered that the intermediate-spin triplet (S = 1) controls the energy of the transition state for C–H cleavage, while the high-spin quintet (S = 2) controls the position of the equilibrium. Na + drives the equilibrium toward oxidative addition due to an electrostatic effect, while K + and Rb + are dominated by a steric effect that favors the iron(0) species. The key role played by nonbonding interactions in the Fe-mediated C–H activation provides a conceptual model for alkali control over organometallic transformations.
A Dicopper Nitrenoid by Oxidation of a Cu'Cu' Core: Synthesis, Electronic Structure, and Reactivity
A dicopper nitrenoid complex was prepared by formal oxidative addition of the nitrenoid fragment to a dicopper(I) center by reaction with the iminoiodinane PhINTs (Ts = tosylate). This nitrenoid complex, (DPFN)Cu 2 (μ-NTs)[NTf 2 ] 2 (DPFN = 2,7-bis(fluorodi(2-pyridyl)methyl)-1,8-naphthyridine), is a powerful H atom abstractor that reacts with a range of strong C–H bonds to form a mixed-valence Cu(I)/Cu(II) μ-NHTs amido complex in the first example of a clean H atom transfer to a dicopper nitrenoid core. In line with this reactivity, DFT calculations reveal that the nitrenoid is best described as an iminyl (NR radical anion) complex. The nitrenoid was trapped by the addition of water to form a mixed-donor hydroxo/amido dicopper(II) complex, which was independently obtained by reaction of a Cu 2 (μ-OH) 2 complex with an amine through a protonolysis pathway. Furthermore, this mixed-donor complex is an analogue for the proposed intermediate in copper-catalyzed Chan–Evans–Lam coupling, which proceeds via C–X (X = N or O) bond formation. Treatment of the dicopper(II) mixed donor complex with MgPh 2 (THF) 2 resulted in generation of a mixture that includes both phenol and a previously reported dicopper(I) bridging phenyl complex, illustrating that both reduction of dicopper(II) to dicopper(I) and concomitant C–X bond formation are feasible.
Exponential approximation for one-component Yukawa plasma
A theory based on the exponential approximation of the liquid-state theory is applied to study properties of several models of one-component Yukawa plasma characterized by different values of the screening parameter z. The results of the new theory are compared to the results of a conventional theory, which is based on the first-order mean spherical approximation, and to the results of a Monte Carlo simulation. The new theory shows improvements in the predictions for the thermodynamic and structural properties of Yukawa plasmas with high and intermediate values of the screening parameter, z, and coupling parameter, Γ. For low values of z and Γ, the new theory is comparable in accuracy to the conventional theory, which in turn agrees well with the results of the Monte Carlo simulation.
Preparation of high orbital angular momentum Rydberg states by optical-millimeter-wave STIRAP
Rydberg states of molecules are intrinsically challenging to study due to the presence of fast non-radiative decay pathways, such as predissociation. However, selectively exciting Rydberg states with values of the orbital angular momentum (ℓ) ℓ ≳ 3 is a productive strategy to minimize this rapid decay and to populate molecular Rydberg states with lifetimes that approach those of atoms. Here, in this proof-of-principle demonstration, we transfer population to an nf Rydberg state of the calcium atom by stimulated Raman adiabatic passage, in which an optical and a millimeter-wave field couple the initial and final states via an intermediate nd Rydberg state. Numerical simulations reproduce the observed time and frequency dependences of the population transfer and suggest the utility of this scheme to populate high-ℓ Rydberg states of molecules.
Quantum interference in a four-level system of a {sup 87}Rb atom: Effects of spontaneously generated coherence
In this work, the effects of quantum interference and spontaneously generated coherence (SGC) are theoretically analyzed in a four-level system of a {sup 87}Rb atom. For the effects of SGC, we find that a new kind of electromagnetically induced transparency channel can be induced due to destructive interference, and the nonlinear Kerr absorption can be coherently narrowed or eliminated under different strengths of the coupling and switching fields.
Simultaneous control of two four-wave-mixing fields via atomic spin coherence
We report the experimental observation of simultaneous control of two four-wave-mixing fields via an induced atomic spin coherence formed by a Raman process with one coupling field and one probe field in a triple-{Lambda}-type {sup 85}Rb atomic system. It is shown that by changing the atomic density, intensity, or detuning of the coupling field, the relative intensities of the two four-wave-mixing fields can be manipulated. This behavior can be explained as the change in the spin coherence for varying the coupling field intensity and the large difference in the attenuation coefficients of the two produced four-wave-mixing fields for varying the atomic density. This controlling process may find applications in coherent control of nonlinear optical processes and quantum information processing.
Above-threshold multiphoton photoemission from noble metal surfaces
Exciting solids with intense femtosecond laser pulses prompts electrons of the interrogated material to respond in a highly nonlinear manner, as is evident in the emission of high-order harmonic radiation and photoelectrons with kinetic energies well above that of the driving photons. Such high-field interactions can be resolved, for example, in above-threshold multiphoton photoemission (ATP) spectroscopy. In this work, we interrogate the nonlinear photoelectric responses of the pristine copper, silver, and gold noble metal surfaces in (111) and (100) crystal orientations in the perturbative regime. Using multiphoton photoemission spectroscopy (mPP) excited by finely tuned optical fields, we characterize enhancement of the mPP and ATP yields from (111) surfaces in selected k||-momentum ranges when the occupied Shockley surface (SS) states are (near-)resonantly coupled by multiphoton transitions to image potential (IP) intermediate states in the excitation process. The ATP signal from the IP states of (111) surfaces is largely defined by their formation through polarization of SS electrons; this observation is contrasted with ATP experiments from the Ag(100) surface, for which the SS becomes an unoccupied resonance and the IP states can only be excited from bands with significantly more bulk character. In addition, based on the optical power and nonlinear order-dependent mPP spectra, we provide evidence for ATP being a one-step, rather than a sequential process, as previously postulated.
Structural basis of the amidase ClbL central to the biosynthesis of the genotoxin colibactin
Colibactin is a genotoxic natural product produced by select commensal bacteria in the human gut microbiota. The compound is a bis-electrophile that is predicted to form interstrand DNA cross-links in target cells, leading to double-strand DNA breaks. The biosynthesis of colibactin is carried out by a mixed NRPS–PKS assembly line with several noncanonical features. An amidase, ClbL, plays a key role in the pathway, catalyzing the final step in the formation of the pseudodimeric scaffold. ClbL couples α-aminoketone and β-ketothioester intermediates attached to separate carrier domains on the NRPS–PKS assembly. Here, the 1.9 Å resolution structure of ClbL is reported, providing a structural basis for this key step in the colibactin biosynthetic pathway. The structure reveals an open hydrophobic active site surrounded by flexible loops, and comparison with homologous amidases supports its unusual function and predicts macromolecular interactions with pathway carrier-protein substrates. Modeling protein–protein interactions supports a predicted molecular basis for enzyme–carrier domain interactions. Overall, the work provides structural insight into this unique enzyme that is central to the biosynthesis of colibactin.
Template-guided self-assembly of discrete optoplasmonic molecules and extended optoplasmonic arrays
The integration of metallic and dielectric building blocks into optoplasmonic structures creates new electromagnetic systems in which plasmonic and photonic modes can interact in the near-, intermediate- and farfield. The morphology-dependent electromagnetic coupling between the different building blocks in these hybrid structures provides a multitude of opportunities for controlling electromagnetic fields in both spatial and frequency domain as well as for engineering the phase landscape and the local density of optical states. Control over any of these properties requires, however, rational fabrication approaches for well-defined metal-dielectric hybrid structures. Template-guided self-assembly is a versatile fabrication method capable of integrating metallic and dielectric components into discrete optoplasmonic structures, arrays, or metasurfaces. The structural flexibility provided by the approach is illustrated by two representative implementations of optoplasmonic materials discussed in this review. In optoplasmonic atoms or molecules optical microcavities (OMs) serve as whispering gallery mode resonators that provide a discrete photonic mode spectrum to interact with plasmonic nanostructures contained in the evanescent fields of the OMs. In extended hetero-nanoparticle arrays in-plane scattered light induces geometry-dependent photonic resonances that mix with the localized surface plasmon resonances of the metal nanoparticles. As a result, we characterize the fundamental electromagnetic working principles underlying both optoplasmonic approaches and review the fabrication strategies implemented to realize them.
Collaborative Research: Regional climate-change projections through next-generation empirical and dynamical models (Final Technical Report)
This is the final report for a DOE-funded research project describing the outcome of research on non-homogeneous hidden Markov models (NHMMs) and coupled ocean-atmosphere (O-A) intermediate-complexity models (ICMs) to identify the potentially predictable modes of climate variability, and to investigate their impacts on the regional-scale. The main results consist of extensive development of the hidden Markov models for rainfall simulation and downscaling specifically within the non-stationary climate change context together with the development of parallelized software; application of NHMMs to downscaling of rainfall projections over India; identification and analysis of decadal climate signals in data and models; and, studies of climate variability in terms of the dynamics of atmospheric flow regimes.
Microstructure, Mechanical Properties, Hot-Die Forming, and Joining of 47XD Gamma TiAl Rolled Sheets
The microstructure and mechanical properties, along with the hot-die forming and joining of Ti-47Al-2Nb-2Mn-0.8 vol% TiB, sheets (known as 47XD), produced by a low-cost rolling process, were evaluated. A near-gamma microstructure was obtained in the as-rolled condition. The microstructures of heat-treated sheets ranged from a recrystallized equiaxed near-gamma microstructure at 1,200 to 1,310 C, to a duplex microstructure at 1,350 C, to a fully lamellar microstructure at 1,376 C. Tensile behavior was determined for unidirectionally rolled and cross-rolled sheets for room temperature (RT) to 816 C. Yield stress decreased gradually with increasing deformation temperature up to 704 C; above 704 C, it declined rapidly. Ultimate tensile strength exhibited a gradual decrease up to 537 C before peaking at 704 C, followed by a rapid decline at 816 C. The modulus showed a gradual decrease with temperature, reaching approximately 72% of the RT value at 816 C. Strain to failure increased slowly from RT to 537 C; between 537 C and 704 C it exhibited a phenomenal increase, suggesting that the ductile-brittle transition temperature was below 704 C. Fracture mode changed from transgranular fracture at low temperature, to a mixture of transgranular and intergranular fracture at intermediate temperature, to ductile fracture at 816 C, coupled with dynamic recrystallization at large strains. Creep rupture response was evaluated between 649 and 816 C over the stress range of 69 to 276 MPa. Deformation parameters for steady-state creep rate and time-to-rupture were similar: activation energies of approximately 350 kJ/mol and stress exponents of approximately 4.5. Hot-die forming of sheets into corrugations was done at elevated temperatures in vacuum. The process parameters to join sheets by diffusion bonding and brazing with TiCuNi 70 filler alloy were optimized for test coupons and successfully used to fabricate large truss-core and honeycomb structures. Nondestructive evaluation methods, e.g., ultrasonic C-scans and thermography along with metallography, were used to characterize bond quality. Microstructural evaluation during heat treatment, identification of phases at the braze/matrix interface, determination of shear strengths of brazed joints, and deformation mechanisms during tensile and creep processes will be discussed.
Methods and systems for the production of hydrogen
Methods and systems are disclosed for the production of hydrogen and the use of high-temperature heat sources in energy conversion. In one embodiment, a primary loop may include a nuclear reactor utilizing a molten salt or helium as a coolant. The nuclear reactor may provide heat energy to a power generation loop for production of electrical energy. For example, a supercritical carbon dioxide fluid may be heated by the nuclear reactor via the molten salt and then expanded in a turbine to drive a generator. An intermediate heat exchange loop may also be thermally coupled with the primary loop and provide heat energy to one or more hydrogen production facilities. A portion of the hydrogen produced by the hydrogen production facility may be diverted to a combustor to elevate the temperature of water being split into hydrogen and oxygen by the hydrogen production facility.
The EGS Collab Hydroshear Experiment at the Sanford Underground Research Facility – Siting Criteria and Evaluation of Candidate Sites
The objective of the EGS Collab project is to establish a suite of intermediate-scale (~10-20 m) field test beds coupled with stimulation and interwell flow tests to provide a basis to better understand fracture stimulation methods, resulting fracture geometries, and processes that control heat transfer between rock and stimulated fractures. Experiment 1 of the project is being conducted at a depth of ~1.5 km in the Sanford Underground Research Facility (SURF) on the 4850 Level (ft. below the ground surface). The stimulation method planned for Experiment 2 of this project is hydroshearing of an existing natural fracture. In siting this experiment, there are several key geologic criteria that need to be met. These include: 1) the fracture should be least 10 m in length so that it could be intersected by two boreholes that are spaced that far apart; 2) it should be optimally oriented relevant to the stress field so that it is critically stressed; 3) the site should have appropriate stress conditions (not too shallow a depth); 4) the fracture should have sufficient permeability to allow for prestimulation flow testing, but not too high a permeability that would preclude permeability enhancement via shear stimulation; 5) the fracture should not intersect other features (permeable fractures, boreholes, adjacent drifts) that could serve as major leak-off zones; 6) the site should not be complicated by geology (a single lithology would be preferred). In addition, there are logistical criteria that will also influence site selection, including: 1) site availability/access, 2) logistical support, e.g., power, internet, water, operating rail system; 3) drift size and orientation compatible with drilling and site operations; 4) appropriate ground support. There are only two deep levels at SURF that can be accessed by the Yates Shaft: the 4100 and the 4850, so we limited our search to these two levels. Currently, three candidate sites are being evaluated: the existing Experiment 1 site and its surroundings on the West Drift on the 4850 level, and two locations on the 4100 level. This paper will evaluate advantages, disadvantages, and risks associated with these three options at SURF.
The distribution, orientation, and characteristics of natural fractures for Experiment 1 of the EGS Collab Project, Sanford Underground Research Facility
The EGS Collab project is focused on understanding and predicting permeability enhancement and evolution in crystalline rocks. To accomplish this, the project is creating a suite of intermediate-scale (~10-20 m) field test beds coupled with stimulation and interwell flow tests that will provide a basis to better understand the fracture geometries and processes that control heat transfer between rock and stimulated fractures. As part of the site characterization effort for the first experimental test bed, our team has worked on mapping the distribution, orientation, and nature of open and healed fractures exposed along the drift wall and within the eight bore holes drilled for this test bed. The fractures have been characterized through detailed description of continuous cores obtained from these boreholes, evaluation of televiewer logs, and mapping of fractures and seeps exposed along the drift wall. The fracture data are being compiled and interpreted for slip and dilation tendencies, and will be incorporated into coupled-process geomechanical flow and transport models to better constrain the planned flow and tracer tests.
ChemComp: Compiling and Computing with Chemical Reaction Networks
The exponential growth in computing demands driven by scientific computing, data analytics, and artificial intelligence is pushing conventional CMOS-based high-performance computing systems to their physical and energy efficiency limits. As we approach the era of post-exascale computing, disruptive approaches are necessary to overcome these barriers and achieve substantial gains in energy efficiency. Analog and hybrid digital-analog computing systems have emerged as promising alternatives, offering the potential for orders-of-magnitude improvements in efficiency. Among these, biochemical computing stands out as a novel paradigm capable of leveraging the natural efficiency of chemical reactions, which have shown promise in solving optimization problems by converging to steady states. By scaling up reaction networks or reaction vessel sizes, biochemical systems present an opportunity to meet the high-performance demands of modern computing tasks. Despite their promise, significant theoretical and practical challenges remain, particularly in formulating and mapping computational problems to chemical reaction networks (CRNs) and designing viable biochemical computing devices. This paper addresses these challenges by introducing new ideas to ChemComp, a compilation and emulation framework for chemical computation. This work describes the mechanisms through which solutions to ordinary differential equations (ODEs) that can be represented as CRN systems can be achieved. Furthermore, we explain the design principles of an ODE dialect implemented as a multi-level intermediate representation (MLIR) compiler extension that will be coupled with existing infrastructure. We demonstrate the potential of our framework through a case study emulating a simplified chemical reservoir computing device. This work establishes foundational tools and methodologies necessary to harness the computational power of chemistry, paving the way for the development of energy-efficient, high-performance computing systems tailored to contemporary and future computational needs.
TiO 2 Nanoparticles Enabling Photocatalytic Desulfurization for C–C Coupling Reaction Using Visible Light
We uncover a surface-mediated mechanism for visible-light-driven photocatalytic desulfurization of thiols on titanium dioxide (TiO 2 ) nanoparticles under LED illumination (>420 nm). Combined diffuse reflectance, infrared, and cryogenic electron paramagnetic resonance spectroscopy verify the formation of a surface thiol–Ti charge-transfer complex that introduces visible-light absorption into an otherwise UV-active reaction system. Selective photoexcitation of this surface complex drives interfacial charge transfer, directly activating the adsorbed thiol and inducing C–S bond scission without the band gap excitation of TiO 2 . The resulting carbon-centered radical intermediates are intercepted by styrene to form C–C coupling products. These results uncover a distinct surface-mediated photocatalytic mechanism in which charge-transfer complex formation governs both light absorption and chemical activation, providing a mechanistic framework for extending visible-light reactivity to wide-bandgap metal oxide photocatalysts.
Reduced dynamic complexity allows structure elucidation of an excited state of KRAS G13D
Localized dynamics of RAS, including regions distal to the nucleotide-binding site, is of high interest for elucidating the mechanisms by which RAS proteins interact with effectors and regulators and for designing inhibitors. Among several oncogenic mutants, methyl relaxation dispersion experiments reveal highly synchronized conformational dynamics in the active (GMPPNP-bound) KRAS G13D , which suggests an exchange between two conformational states in solution. Methyl and 31 P NMR spectra of active KRAS G13D in solution confirm a two-state ensemble interconverting on the millisecond timescale, with a major Pγ atom peak corresponding to the dominant State 1 conformation and a secondary peak indicating an intermediate state different from the known State 2 conformation recognized by RAS effectors. High-resolution crystal structures of active KRAS G13D and KRAS G13D -RAF1 RBD complex provide snapshots of the State 1 and 2 conformations, respectively. We use residual dipolar couplings to solve and cross-validate the structure of the intermediate state of active KRAS G13D , showing a conformation distinct from those of States 1 and 2 outside the known flexible switch regions. The dynamic coupling between the conformational exchange in the effector lobe and the breathing motion in the allosteric lobe is further validated by a secondary mutation in the allosteric lobe, which affects the conformational population equilibrium.