Strongly coupled electronic, magnetic, and lattice degrees of freedom in LaCo[subscript 5] under pressure
Abstract not provided
Stillwell, Ryan L.↗
SEARCH · Engineering Papers
Results for “Electronic coupling”
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Effects of electron-phonon coupling and electronic thermal conductivity in high energy molecular dynamics simulations of irradiation cascades in nickel
The two-temperature model has been applied to investigate the effects of the electronic subsystem on 150 keV Ni ion cascades in nickel using molecular dynamics simulation. We explore the effects of the magnitude of the electron-phonon coupling and the electronic thermal conductivity on defect production and cluster formation. It has been found that stronger electron-phonon coupling allows larger and more rapid energy feedback to the atomic subsystem, leading to reduction of number of point defects and suppression of the formation of larger defect clusters. It was observed that larger electronic thermal conductivity results in slightly increased number of point defects and larger size vacancy clusters. The latter takes place because of suppression of point defects recombination in faster cooling areas of initial damage.
Zarkadoula, Eva↗
Crystal structure of the pristine peroxidase ferryl center and its relevance to proton-coupled electron transfer
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Chreifi, Georges↗
Theoretical analysis of the sequential proton-coupled electron transfer mechanisms for H2 oxidation and production pathways catalyzed by nickel molecular electrocatalysts
The design of electrocatalysts for the oxidation and production of H2 is important for the development of alternative energy sources. This paper focuses on the electrocatalysts, where denotes 1,5-diaza-3,7-diphosphacyclooctane ligands with substituent groups R and R' covalently bound to the phosphorus and nitrogen atoms, respectively. Theoretical methods are used to investigate the mechanism of the step in the catalytic cycle corresponding to – e– → for H2 oxidation and the reverse reaction for H2 production. This step involves electron transfer (ET) between the Ni complex and the electrode as well as proton transfer (PT) between the Ni and the N. The sequential mechanisms, PT–ET and ET–PT, are investigated for the following (R,R’) substituents: (Me,Me), (Ph,Ph), and (Ph,Bz), where Me, Ph, and Bz denote methyl, phenyl, and benzyl substituents. Density functional theory is used to calculate reduction potentials, pKas, and PT pathways, and Marcus theory is used to describe the electrochemical electron transfer, including the effects of solute and solvent reorganization energies. For the (Ph,Ph) and (Ph,Bz) systems, the sequential PT–ET mechanism would require surmounting a large free energy barrier for the initial PT step, followed by thermodynamically favorable or thermoneutral ET. The sequential ET–PT mechanism for these systems would require a relatively large initial applied overpotential, followed by a PT reaction with a relatively low free energy barrier. Consistent with experimental data, the calculated overpotential required for the initial reduction in the ET–PT mechanism is lower for the (Ph,Bz) system than for the (Ph,Ph) system. The concerted mechanism, in which the electron and proton transfer simultaneously without a stable intermediate, may be thermodynamically favorable and is a direction of future research. This material is based upon work supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under FWP56073.
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
Proton-Coupled Electron Transfer in a Strongly Coupled Photosystem II-Inspired Chromophore–Imidazole–Phenol Complex: Stepwise Oxidation and Concerted Reduction
Proton-coupled electron-transfer (PCET) reactions were studied in acetonitrile for a Photosystem II (PSII) inspired [Ru(bpy) 2 (phen-imidazole-Ph(OH)( t Bu) 2 )] 2+ , in which Ru(III) generated by a flash-quench sequence oxidizes the appended phenol and the proton is transferred to the hydrogen bonded imidazole base. In contrast to related systems, the donor and acceptor are strongly coupled, as indicated by the shift in the Ru III/II couple upon phenol oxidation, and intramolecular oxidation of the phenol by Ru(III) is energetically favorable by both stepwise or concerted pathways. The phenol oxidation occurs via a stepwise ET-PT mechanism with k ET = 2.7 × 10 7 s ₋1 and a kinetic isotope effect (KIE) of 0.99 ± 0.03. The electron transfer reaction was characterized as adiabatic with λ DA = 1.16 eV and 280 < H DA < 540 cm ₋1 consistent with strong electronic coupling and slow solvent dynamics. Reduction of the phenoxyl radical by the quencher radical was examined as the analogue of the redox reaction between the PSII tyrosyl radical and the oxygen evolving complex (OEC). In our PSII-inspired complex, the recombination reaction activation energy is < 2 kcal mol ₋1 . In conclusion, the reaction is nonadiabatic (V PCET ~ 22 cm ₋1 (H) and 49 cm ₋1 (D)), concerted, and exhibits an unexpected inverse KIE of 0.55 that is attributed to greater overlap of the reactant vibronic ground state with the OD vibronic states of the proton acceptor due to the smaller quantum spacing of the deuterium vibrational levels.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Kinetics teach that electronic coupling lowers the free-energy change that accompanies electron transfer
Significance Nature’s use of electronic coupling (H DA ) and free-energy (ΔG o ) gradients to vectorially control electron transport provides inspiration for artificial photosynthesis. Theoretical predictions indicate that H DA and ΔG o are not independent parameters, and are instead linked. Reported here is a broadly applicable kinetic approach that was utilized to demonstrate such behavior for four acceptor–bridge–donor compounds. When the electronic coupling was large and electron transfer was adiabatic, the free energy of the reaction |ΔG o | was less than that for nonadiabatic transfer. This finding should be taken into account in the design of hybrid materials for solar energy conversion and has broad implications to the many classes of electron-transfer reactions in biology and chemistry.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Turn-On Conductivity with Proton-Coupled Electron Transport in Metal–Organic Frameworks
Proton-coupled electron transfer (PCET) has been studied for decades in the context of molecular reactivity, but its impact on long-range electron transport is barely understood. When defined broadly as ion-coupled charge transport (ICCT), relevant systems include lithium-ion battery electrodes, electrochromic coatings, and myriad electrocatalysts. Despite ample evidence that ion-electron coupling enhances or diminishes the performance of these devices, little is known about the experimental signatures of ICCT and the microscopic factors that govern its mechanism. Here, we expect that ion-electron coupling becomes especially relevant in high surface area materials, such as the layered electrodes of intercalation batteries, due to the close proximity of itinerant electrons and electrolyte. Here, we report an electrochemical investigation into a family of metal-organic frameworks (MOFs) that serves as a well-defined platform for understanding the effect of ICCT on both elec- tronic and ionic conductivity. Through photochemical doping of e - –H + pairs and introduction of solvent guest molecules, the Ti-containing MOFs convert from electronic-only insulators conductors (σ e ≈ 10 -12 S cm -1 ) to mixed ion-electron semiconduc- tors (σ e ≈ 10 -7 S cm -1 , σ ion ≈ 10 -5 S cm -1 ). Direct current and alternating current techniques support the existence of proton- electron coupling and, critically, that improved ionic conductivity enhances electronic conductivity. Taken together, these results provide direct evidence that PCET enables long-range charge transport and generalized electrochemical tools and synthetic methods for studying ion-electron coupling in materials broadly.
Charge transport↗
Theoretical Modeling of Electrochemical Proton-Coupled Electron Transfer
Proton-coupled electron transfer (PCET) plays an essential role in a wide range of electrocatalytic processes. Here, a vast array of theoretical and computational methods have been developed to study electrochemical PCET. These methods can be used to calculate redox potentials and pKa values for molecular electrocatalysts, proton-coupled redox potentials and bond dissociation free energies for PCET at metal and semiconductor interfaces, and reorganization energies associated with electrochemical PCET. Periodic density functional theory can also be used to compute PCET activation energies and perform molecular dynamics simulations of electrochemical interfaces. Various approaches for maintaining a constant electrode potential in electronic structure calculations and modeling complex interactions in the electric double layer (EDL) have been developed. Theoretical formulations for both homogeneous and heterogeneous electrochemical PCET spanning the adiabatic, nonadiabatic, and solvent-controlled regimes have been developed and provide analytical expressions for the rate constants and current densities as functions of applied potential. The quantum mechanical treatment of the proton and inclusion of excited vibronic states have been shown to be critical for describing experimental data, such as Tafel slopes and potential dependent kinetic isotope effects. The calculated rate constants can be used as input to microkinetic models and voltammogram simulations to elucidate complex electrocatalytic processes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Theoretical Analysis of Proton Relays in Electrochemical Proton-Coupled Electron Transfer
The coupling of long-range electron transfer to proton transport over multiple sites plays a vital role in many biological and chemical processes. Recently a molecule with a hydrogen-bond relay inserted between the proton donor and acceptor sites in a proton-coupled electron transfer (PCET) system was studied electrochemically. The standard rate constants and kinetic isotope effects (KIEs) were measured experimentally for this system and a related single proton transfer system. In the present paper, these systems are studied theoretically using vibronically nonadiabatic rate constant expressions for electrochemical PCET. Application of this approach to proton relays requires the calculation of multidimensional proton vibrational wavefunctions and incorporation of multiple proton donor-acceptor motions. The calculated KIEs and relative standard rate constants for the single and double proton transfer systems are in agreement with the experimental data. The calculations indicate that the standard rate constant is lower for the double proton transfer system because of the smaller overlap integral between the ground state reduced and oxidized proton vibrational wavefunctions for this system, resulting in greater contributions from excited electron-proton vibronic states with higher free energy barriers. The decrease in proton donor-acceptor distances due to thermal fluctuations and the contributions from excited electron-proton vibronic states play important roles in proton relay systems. The theory suggests that the PCET rate constant may be increased by decreasing the equilibrium proton donor-acceptor distances or modifying the thermal motions of the molecule to facilitate the concurrent decrease of these distances. The submission of this journal article in ERIA is a requirement of the EFRC subcontract with Pennsylvania State University collaborators to get publications to OSTI.
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
Cooled electronic system with thermal spreaders coupling electronics cards to cold rails
Liquid-cooled electronic systems are provided which include an electronic assembly having an electronics card and a socket with a latch at one end. The latch facilitates securing of the card within the socket or removal of the card from the socket. A liquid-cooled cold rail is disposed at the one end of the socket, and a thermal spreader couples the electronics card to the cold rail. The thermal spreader includes first and second thermal transfer plates coupled to first and second surfaces on opposite sides of the card, and thermally conductive extensions extending from end edges of the plates, which couple the respective transfer plates to the liquid-cooled cold rail. The thermally conductive extensions are disposed to the sides of the latch, and the card is securable within or removable from the socket using the latch without removing the cold rail or the thermal spreader.
42 ENGINEERING↗
Electronic coupling calculations with transition charges, dipoles, and quadrupoles derived from electrostatic potential fitting
A transition charge, dipole, and quadrupole from electrostatic potential (TrESP-CDQ) method for electronic coupling calculations is proposed. The TrESP method is based on the classical description of electronic Coulomb interaction between transition densities for individual molecules. In the original TrESP method, only the transition charge interactions were considered as the electronic coupling. In the present study, the TrESP method is extended to include the contributions from the transition dipoles and quadrupoles as well as the transition charges. Hence, the self-consistent transition density is employed in the ESP fitting procedure. To check the accuracy of the present approach, several test calculations are performed to a helium dimer, a methane dimer, and an ethylene dimer. As a result, the TrESP-CDQ method gives a much improved description of the electronic coupling, compared with the original TrESP method. The calculated results also show that the self-consistent treatment to the transition densities contributes significantly to the accuracy of the electronic coupling calculations. Based on the successful description of the electronic coupling, the contributions to the electronic coupling are also analyzed. This analysis clearly shows a negligible contribution of the transition charge interaction to the electronic coupling. Hence, the distribution of the transition density is found to strongly influence the magnitudes of the transition charges, dipoles, and quadrupoles. The present approach is useful for analyzing and understanding the mechanism of excitation-energy transfer.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Variation of Energy Density of States in Quantum Dot Arrays due to Interparticle Electronic Coupling
Subnanometer-resolved local electron energy structure was measured in PbS quantum dot superlattice arrays using valence electron energy loss spectroscopy with scanning transmission electron microscopy. We found smaller values of the lowest available transition energies and an increased density of electronic states in the space between quantum dots with shorter interparticle spacing, indicating extension of carrier wave functions as a result of interparticle electronic coupling. Lastly, a quantum simulation verified both trends and illustrated the wave function extension effect.
36 MATERIALS SCIENCE↗
Importance of the tuning of band position in optimizing the electronic coupling and photocatalytic activity of nanocomposite
The electronic coupling and photocatalytic activity of Ag{sub 2}CO{sub 3}–TiO{sub 2} nanocomposite can be optimized by the fine-tuning of the band position of titanium oxide with nitrogen doping. The increase of the valence band energy of TiO{sub 2} by N-doping leads not only to the enhanced absorption of visible light but also to the promoted hole transfer from Ag{sub 2}CO{sub 3} to TiO{sub 2}, resulting in the efficient spatial separation of photogenerated electrons and holes. While the undoped Ag{sub 2}CO{sub 3}–TiO{sub 2} nanocomposite shows an inferior photocatalytic activity to the pure Ag{sub 2}CO{sub 3}, the photocatalyst performance of N-doped nanocomposite is better than those of Ag{sub 2}CO{sub 3} and undoped Ag{sub 2}CO{sub 3}–TiO{sub 2} nanocomposite. This observation underscores a significant enhancement of the photocatalytic activity of nanocomposite upon N-doping, a result of enhanced electronic coupling between the hybridized species. The present results clearly demonstrate the importance of the fine-tuning of band position in optimizing the photocatalytic activity of hybrid-type photocatalysts. - Highlights: • The band position of Ag{sub 2}CO{sub 3}–TiO{sub 2} can be effectively tailored by nitrogen doping. • The N-doping leads to the improvement of charge separation. • The N-doped Ag{sub 2}CO{sub 3}–TiO{sub 2} shows high photocatalytic activity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Critical analysis of fragment-orbital DFT schemes for the calculation of electronic coupling values
We present a critical analysis of the popular fragment-orbital density-functional theory (FO-DFT) scheme for the calculation of electronic coupling values. We discuss the characteristics of different possible formulations or “flavors” of the scheme which differ by the number of electrons in the calculation of the fragments and the construction of the Hamiltonian. In addition to two previously described variants based on neutral fragments, we present a third version taking a different route to the approximate diabatic state by explicitly considering charged fragments. In applying these FO-DFT flavors to the two molecular test sets HAB7 (electron transfer) and HAB11 (hole transfer), we find that our new scheme gives improved electronic couplings for HAB7 (−6.2% decrease in mean relative signed error) and greatly improved electronic couplings for HAB11 (−15.3% decrease in mean relative signed error). A systematic investigation of the influence of exact exchange on the electronic coupling values shows that the use of hybrid functionals in FO-DFT calculations improves the electronic couplings, giving values close to or even better than more sophisticated constrained DFT calculations. Comparing the accuracy and computational cost of each variant, we devise simple rules to choose the best possible flavor depending on the task. For accuracy, our new scheme with charged-fragment calculations performs best, while numerically more efficient at reasonable accuracy is the variant with neutral fragments.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Influences of Quantum Mechanically Mixed Electronic and Vibrational Pigment States in 2D Electronic Spectra of Photosynthetic Systems: Strong Electronic Coupling Cases
In 2D electronic spectroscopy studies, long-lived quantum beats have recently been observed in photosynthetic systems, and several theoretical studies have suggested that the beats are produced by quantum mechanically mixed electronic and vibrational states. Concerning the electronic-vibrational quantum mixtures, the impact of protein-induced fluctuations was examined by calculating the 2D electronic spectra of a weakly coupled dimer with the Franck-Condon active vibrational modes in the resonant condition. This analysis demonstrated that quantum mixtures of the vibronic resonance are rather robust under the influence of the fluctuations at cryogenic temperatures, whereas the mixtures are eradicated by the fluctuations at physiological temperatures. However, this conclusion cannot be generalized because the magnitude of the coupling inducing the quantum mixtures is proportional to the inter-pigment electronic coupling. In this paper, we explore the impact of the fluctuations on electronic-vibrational quantum mixtures in a strongly coupled dimer with an off-resonant vibrational mode. Toward this end, we calculate energy transfer dynamics and 2D electronic spectra of a model dimer that corresponds to the most strongly coupled bacteriochlorophyll molecules in the Fenna-Matthews-Olson complex in a numerically accurate manner. The quantum mixtures are found to be robust under the exposure of protein-induced fluctuations at cryogenic temperatures, irrespective of the resonance. At 300 K, however, the quantum mixing is disturbed more strongly by the fluctuations, and therefore, the beats in the 2D spectra become obscure even in a strongly coupled dimer with a resonant vibrational mode. Further, the overall behaviors of the energy transfer dynamics are demonstrated to be dominated by the environment and coupling between the 0 0 vibronic transitions as long as the Huang-Rhys factor of the vibrational mode is small. Finally, the electronic-vibrational quantum mixtures do not necessarily play a significant role in electronic energy transfer dynamics despite contributing to the enhancement of long-lived quantum beating in the 2D spectra.
2D electronic spectra↗
Probing the axion-electron coupling with NuSTAR observations of galaxies
We search for the existence of ultralight axions coupling to electrons and photons using data from the NuSTAR telescope directed toward the galaxies M82, M87, and M31. We focus on electron bremsstrahlung and Compton scattering for axion production in stars, summing over the stellar populations found in the target galaxies when computing the axion luminosity. We then compute the hard x-ray signal that arises from the conversion of these axions to photons in each galaxy’s magnetic fields, inferred from analog galaxies in cosmological magnetohydrodynamic simulations. Analyzing NuSTAR data toward these galaxies between roughly 20 to 70 keV, we find no evidence for axions and set leading constraints on the combined axion-electron and axion-photon coupling at the level of |𝑔 𝑎𝑒𝑒 ×𝑔 𝑎𝛾𝛾 | ≲ 8.3 ×10 −27 GeV −1 for 𝑚 𝑎 ≲ 10 −10 eV at 95% confidence, with M82 providing the most stringent constraints.
Axion-like particles↗