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At least 1,459 records · Page 81
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Proton-coupled electron transfer across benzimidazole bridges in bioinspired proton wires

Designing molecular platforms for controlling proton and electron movement in artificial photosynthetic systems is crucial to efficient catalysis and solar energy conversion. The transfer of both protons and electrons during a reaction is known as proton-coupled electron transfer (PCET) and is used by nature in myriad ways to provide low overpotential pathways for redox reactions and redox leveling, as well as to generate bioenergetic proton currents. Herein, we describe theoretical and electrochemical studies of a series of bioinspired benzimidazole-phenol (BIP) derivatives and a series of dibenzimidazole-phenol (BI 2 P) analogs with each series bearing the same set of terminal proton-accepting (TPA) groups. The set of TPAs spans more than 6 pK a units. These compounds have been designed to explore the role of the bridging benzimidazole(s) in a one-electron oxidation process coupled to intramolecular proton translocation across either two (the BIP series) or three (the BI 2 P series) acid/base sites. These molecular constructs feature an electrochemically active phenol connected to the TPA group through a benzimidazole-based bridge, which together with the phenol and TPA group form a covalent framework supporting a Grotthuss-type hydrogen-bonded network. Infrared spectroelectrochemistry demonstrates that upon oxidation of the phenol, protons translocate across this well-defined hydrogen-bonded network to a TPA group. The experimental data show the benzimidazole bridges are non-innocent participants in the PCET process in that the addition of each benzimidazole unit lowers the redox potential of the phenoxyl radical/phenol couple by 60 mV, regardless of the nature of the TPA group. Using a series of hypothetical thermodynamic steps, density functional theory calculations correctly predicted the dependence of the redox potential of the phenoxyl radical/phenol couple on the nature of the final protonated species and provided insight into the thermodynamic role of dibenzimidazole units in the PCET process. This information is crucial for developing molecular “dry proton wires” with these moieties, which can transfer protons via a Grotthuss-type mechanism over long distances without the intervention of water molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Dynamic signatures of electronically nonadiabatic coupling in sodium hydride: a rigorous test for the symmetric quasi-classical model applied to realistic, ab initio electronic states in the adiabatic representation

Sodium hydride (NaH) in the gas phase presents a seemingly simple electronic structure making it a potentially tractable system for the detailed investigation of nonadiabatic molecular dynamics from both computational and experimental standpoints. The single vibrational degree of freedom, as well as the strong nonadiabatic coupling that arises from the excited electronic states taking on considerable ionic character, provides a realistic chemical system to test the accuracy of quasi-classical methods to model population dynamics where the results are directly comparable against quantum mechanical benchmarks. Here, using a simulated pump–probe type experiment, this work presents computational predictions of population transfer through the avoided crossings of NaH via symmetric quasi-classical Meyer–Miller (SQC/MM), Ehrenfest, and exact quantum dynamics on realistic, ab initio potential energy surfaces. The main driving force for population transfer arises from the ground vibrational level of the D 1 Σ + adiabatic state that is embedded in the manifold of near-dissociation C 1 Σ + vibrational states. When coupled through a sharply localized first-order derivative coupling most of the population transfers between t = 15 and t = 30 fs depending on the initially excited vibronic wavepacket. While quantum mechanical effects are expected due to the reduced mass of NaH, predictions of the population dynamics from both the SQC/MM and Ehrenfest models perform remarkably well against the quantum dynamics benchmark. Additionally, an analysis of the vibronic structure in the nonadiabatically coupled regime is presented using a variational eigensolver methodology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Electronically-coupled redox centers in trimetallic cobalt complexes

Synthesis and isolation of molecular building blocks of metal–organic frameworks (MOFs) can provide unique opportunities for characterization that would otherwise be inaccessible due to the heterogeneous nature of MOFs. Herein, we report a series of trinuclear cobalt complexes incorporating dithiolene ligands, triphenylene-2,3,6,7,10,11-hexathiolate (THT) (1 3+ ), and benzene hexathiolate (BHT) (2 3+ ), with 1,1,1,-tris(diphenylphosphinomethyl)ethane (triphos) employed as the capping ligand. Single crystal X-ray analyses of 1 3+ and 2 3+ display three five-coordinate cobalt centers bound to the triphos and dithiolene ligands in a distorted square pyramidal geometry. Cyclic voltammetry studies of 1 3+ and 2 3+ reveal three redox features associated with the formation of mixed valence states due to the sequential reduction of the redox-active metal centers (Co III/II ). Using this electrochemical data, the comproportionality values were determined for 1 and 2 (log K c = 1.4 and 1.5 for 1, and 4.7 and 5.8 for 2), suggesting strong resonance-stabilized coupling of the metal centers, with stronger electronic coupling observed for complex 2 compared to that for complex 1. Cyclic voltammetry studies were also performed in solvents of varying polarity, whereupon the difference in the standard potentials (ΔE 1/2 ) for 1 and 2 was found to shift as a function of the polarity of the solvent, indicating a negative correlation between the dielectric constant of the electrochemical medium and the stability of the mixed valence species. Spectroelectrochemical studies of in situ generated multi-valent (MV) states of complexes 1 and 2 display characteristic NIR intervalence charge transfer (IVCT) bands, and analysis of the IVCT transitions for complex 2 suggests a weakly coupled class II multi-valent species and relatively large electronic coupling factors (1700 cm –1 for the first multi-valent state of 2 2+ , and 1400 and 4000 cm –1 for the second multi-valent state of 2 + ). Here, density functional theory (DFT) calculations indicate a significant deviation in relative energies of the frontier orbitals of complexes 1 3+ , 2 3+ , and 3 + that contrasts those calculated for the analogous trinuclear cobalt dithiolene complexes employing pentamethylcyclopentadienyl (Cp*) as the capping ligand (Co 3 Cp* 3 THT and Co 3 Cp* 3 BHT, respectively), and may be a result of the cationic nature of complexes 1 3+ , 2 3+ , and 3 + .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Ferroic phase transitions and magnetoelectric coupling in cobalt doped BaTiO 3

Magnetoelectric (ME) materials exhibit interesting physics with cross coupling between ferroelectric and magnetic order parameters and thus strong potential to be utilized in memory, spintronics and other multifunctional electronic/magnetic devices. Doping of suitable transition metals in ferroelectrics can induce magnetism and ME coupling and modify the physical properties. Here, we report the structural, electronic, magnetic and ME coupling of 3.5, 5 and 7.5 mol% cobalt doped BaTiO 3 (BTO) ceramics. X-ray diffraction and Raman spectroscopy indicate that the samples are single phase having a tetragonal crystal structure with P4mm symmetry. The tetragonality ratio is found to decrease with increasing cobalt content. We observed a Fano-like asymmetric peak in the [A 1 (LO 1 )] Raman mode at ~173 cm -1 in all the cobalt doped BTO samples. The cobalt dopants are shown to be uniformly distributed throughout the surface of the samples. We observed a lowering of the ferroelectric transition temperature and increasing diffusivity parameter with increasing cobalt concentration. The electrical properties of all the samples have been investigated in detail by impedance spectroscopy and ac conductivity studies before and after the ferroelectric phase transitions. All the samples show hysteretic ferroelectric behavior with a clear saturation state that decreases with increasing cobalt content. The observed ferroelectricity in these samples is intrinsic in nature. The 3.5% cobalt doped BTO sample exhibits paramagnetic behavior whereas the 5 and 7.5% cobalt doped BTO samples show ferromagnetic ordering below 43 K. The 7.5% cobalt doped BTO samples show significant ME coupling.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Resonance plasmonic coupling: selective enhancement of band edge emission over trap state emission of CdSe quantum dots

The photoluminescence properties of quantum dots (QDs) are often enhanced by eliminating surface trap states through chemical methods. Alternatively, a physical approach is presented here for improving photoluminescence purity in QDs by employing frequency-specific plasmon resonance coupling. Emitter-bound plasmonic hybrids are designed by electrostatically binding negatively charged QDs in water to positively charged gold nanoparticles having a thin polymer coating. Herein, two types of QDs are used: (i) bare CdSe, which exhibits both band edge and trap state emission, and (ii) CdSe overcoated with a ZnS shell (CdSe/ZnS) devoid of trap state emission. Tuning the extinction spectrum of the plasmonic system to match the band edge emission of CdSe enables the selective enhancement of band edge emission over trap state emission. Excellent match in the extinction spectrum of the gold nanoparticle with both, experimentally calculated photoluminescence enhancement factor and theoretically calculated radiative rate enhancement signifies the role of frequency-specific plasmon resonance coupling. Plasmon-coupled photoluminescence of CdSe/ZnS is further investigated by varying the number density of emitter on the surface of plasmonic nanoparticle. An enhancement in the photoluminescence is observed at a lower emitter density of CdSe/ZnS and the photoluminescence enhancement factor closely follows the plasmon resonance. However, photoluminescence quenching occurs with an increase in CdSe/ZnS due to plasmon-assisted nonradiative energy transfer between nearby QDs, as indicated by a red shift in the PL maximum. These studies establish that resonance plasmonic coupling is a convenient physical strategy for tuning the intrinsic photoluminescence properties of QDs for various optoelectronic applications.

Paul, Livin↗
DOE OSTI2024

Quarkonium transport in weakly and strongly coupled plasmas

We report on progress in the nonperturbative understanding of quarkonium dynamics inside a thermal plasma. The time evolution of small-size quarkonium is governed by two-point correlation functions of chromoelectric fields dressed with an adjoint Wilson line, known in this context as generalized gluon distributions (GGDs). The GGDs have been calculated in both weakly and strongly coupled plasmas by using perturbative and holographic methods. Strikingly, the results of our calculations for a strongly coupled plasma indicate that the quarkonium dissociation and recombination rates vanish in the transport descriptions that assume quarkonium undergoes Markovian dynamics. However, this does not imply that the dynamics is trivial. As a starting point to explore the phenomenological consequences of the result at strong coupling, we show a calculation of the Y(1 S ) formation probability in time-dependent perturbation theory. This is a first step towards the development of a transport formalism that includes non-Markovian effects, which, depending on how close the as of yet undetermined nonperturbative QCD result of the GGDs is to the strongly coupled N = 4 SYM result, could very well dominate over the Markovian ones in quark-gluon plasma produced at RHIC and the LHC.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2013

Dense strongly coupled plasma in double laser pulse ablation of lithium: Experiment and simulation

In a simple method of low power nano-second double pulsed laser ablation experiment in collinear geometry, formation of high density strongly coupled plasma is demonstrated. Using time-resolved measurements of the Stark broadened line width and line intensity ratio of the emission lines, the density and temperature of the plasma were estimated respectively. In this experiment, it is shown that ions are strongly coupled (ion-ion coupling parameter comes out to be >4). For comparison, both single and double pulsed laser ablations are presented. For the estimated experimental plasma parameters, first principle Langevin dynamics simulation corroborates the existence of a strongly coupled regime.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2013

Photoionization cross section by Stieltjes imaging applied to coupled cluster Lanczos pseudo-spectra

A recently implemented asymmetric Lanczos algorithm for computing (complex) linear response functions within the coupled cluster singles (CCS), coupled cluster singles and iterative approximate doubles (CC2), and coupled cluster singles and doubles (CCSD) is coupled to a Stieltjes imaging technique in order to describe the photoionization cross section of atoms and molecules, in the spirit of a similar procedure recently proposed by Averbukh and co-workers within the Algebraic Diagrammatic Construction approach. Pilot results are reported for the atoms He, Ne, and Ar and for the molecules H{sub 2}, H{sub 2}O, NH{sub 3}, HF, CO, and CO{sub 2}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Evidence of spin phonon coupling in magnetoelectric NiFe{sub 2}O{sub 4}/PMN-PT composite

The coupling of phonon with spin in strain coupled magnetoelectric NiFe{sub 2}O{sub 4} (NFO)/0.65Pb(Mg{sub 1/3}Nb{sub 2/3})O{sub 3}–0.35PbTiO{sub 3} (PMN-PT) composite was investigated by temperature-dependent Raman spectroscopy and magnetic measurements in the range 30–350 °C. Pure NFO shows usual ferromagnetic behaviour in this temperature range while NFO/PMN-PT composite show dramatic change in magnetic moment across ferroelectric transition temperature (T{sub c} ∼ 180 °C) of PMN-PT. The temperature evolution of the Raman spectra for the composite shows significant phonon anomalies in T-site (Fe-O) and O-site (Ni/Fe-O) phonon modes at ferroelectric transition temperature is attributed to spin phonon coupling in NFO/PMN-PT composite. The strain mediated magnetoelectric coupling mechanism in this composite is apparent from the observed spin phonon interaction.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Dynamics of the longitudinal and transverse modes in presence of equilibrium shear flow in a strongly coupled dusty plasma

In strongly coupled limit the general hydrodynamic (GH) model shows that the dusty plasma, acquiring significant rigidity, is able to support the 'shear' like mode [P. K. Kaw and A. Sen, Phys. Plasmas 5, 3552 (1998)]. In presence of velocity shear, this shear like mode is coupled with the dust acoustic mode which is generated by the compressibility effect of the dust fluid due to the finite temperature of the dust, electron and ion fluids. Local dispersion shows the velocity shear is also responsible for the instabilities of the shear mode, acoustic mode, as well as the shear-acoustic coupled mode. The present work, carried out in GH visco-elastic formalism, also gives the clear insight of the instabilities of the coupled mode in non local regime with a hyperbolic tangent velocity shear profile over a finite width.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Manipulating electromagnetic responses of metal wires at the deep subwavelength scale via both near- and far-field couplings

A hybrid coupling model containing both near- and far-field couplings is developed for radiating two-resonator structures. We demonstrate that the near- and far-field couplings make distinguished contributions to electromagnetic responses. Compared to the classical electromagnetically induced transparency configurations, the presence of far-field coupling provides more flexibility in tuning lineshapes. Planar metamaterials composed of metal wires are designed based on this model, and various electromagnetic responses are experimentally observed.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Single to quadruple quantum dots with tunable tunnel couplings

We prepare a gate-defined quadruple quantum dot to study the gate-tunability of single to quadruple quantum dots with finite inter-dot tunnel couplings. The measured charging energies of various double dots suggest that the dot size is governed by the gate geometry. For the triple and quadruple dots, we study the gate-tunable inter-dot tunnel couplings. For the triple dot, we find that the effective tunnel coupling between side dots significantly depends on the alignment of the center dot potential. These results imply that the present quadruple dot has a gate performance relevant for implementing spin-based four-qubits with controllable exchange couplings.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Jeans self gravitational instability of strongly coupled quantum plasma

The Jeans self-gravitational instability is studied for quantum plasma composed of weakly coupled degenerate electron fluid and non-degenerate strongly coupled ion fluid. The formulation for such system is done on the basis of two fluid theory. The dynamics of weakly coupled degenerate electron fluid is governed by inertialess momentum equation. The quantum forces associated with the quantum diffraction effects and the quantum statistical effects act on the degenerate electron fluid. The strong correlation effects of ion are embedded in generalized viscoelastic momentum equation including the viscoelasticity and shear viscosities of ion fluid. The general dispersion relation is obtained using the normal mode analysis technique for the two regimes of propagation, i.e., hydrodynamic and kinetic regimes. The Jeans condition of self-gravitational instability is also obtained for both regimes, in the hydrodynamic regime it is observed to be affected by the ion plasma oscillations and quantum parameter while in the kinetic regime in addition to ion plasma oscillations and quantum parameter, it is also affected by the ion velocity which is modified by the viscosity generated compressional effects. The Jeans critical wave number and corresponding critical mass are also obtained for strongly coupled quantum plasma for both regimes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Nonlinear coupling of left and right handed circularly polarized dispersive Alfvén wave

The nonlinear phenomena are of prominent interests in understanding the particle acceleration and transportation in the interplanetary space. The ponderomotive nonlinearity causing the filamentation of the parallel propagating circularly polarized dispersive Alfvén wave having a finite frequency may be one of the mechanisms that contribute to the heating of the plasmas. The contribution will be different of the left (L) handed mode, the right (R) handed mode, and the mix mode. The contribution also depends upon the finite frequency of the circularly polarized waves. In the present paper, we have investigated the effect of the nonlinear coupling of the L and R circularly polarized dispersive Alfvén wave on the localized structures formation and the respective power spectra. The dynamical equations are derived in the presence of the ponderomotive nonlinearity of the L and R pumps and then studied semi-analytically as well as numerically. The ponderomotive nonlinearity accounts for the nonlinear coupling between both the modes. In the presence of the adiabatic response of the density fluctuations, the nonlinear dynamical equations satisfy the modified nonlinear Schrödinger equation. The equations thus obtained are solved in solar wind regime to study the coupling effect on localization and the power spectra. The effect of coupling is also studied on Faraday rotation and ellipticity of the wave caused due to the difference in the localization of the left and the right modes with the distance of propagation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Transverse coupling property of beam from ECR ion sources

Experimental evidence of the property of transverse coupling of beam from Electron Cyclotron Resonance (ECR) ion source is presented. It is especially of interest for an ECR ion source, where the cross section of extracted beam is not round along transport path due to the magnetic confinement configuration. When the ions are extracted and accelerated through the descending axial magnetic field at the extraction region, the horizontal and vertical phase space strongly coupled. In this study, the coupling configuration between the transverse phase spaces of the beam from ECR ion source is achieved by beam back-tracking simulation based on the measurements. The reasonability of this coupling configuration has been proven by a series of subsequent simulations.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2014

Multi-level coupled cluster theory

We present a general formalism where different levels of coupled cluster theory can be applied to different parts of the molecular system. The system is partitioned into subsystems by Cholesky decomposition of the one-electron Hartree-Fock density matrix. In this way the system can be divided across chemical bonds without discontinuities arising. The coupled cluster wave function is defined in terms of cluster operators for each part and these are determined from a set of coupled equations. The total wave function fulfills the Pauli-principle across all borders and levels of electron correlation. We develop the associated response theory for this multi-level coupled cluster theory and present proof of principle applications. The formalism is an essential tool in order to obtain size-intensive complexity in the calculation of local molecular properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

The coupled nonlinear dynamics of a lift system

Coupled lateral and longitudinal vibrations of suspension and compensating ropes in a high-rise lift system are often induced by the building motions due to wind or seismic excitations. When the frequencies of the building become near the natural frequencies of the ropes, large resonance motions of the system may result. This leads to adverse coupled dynamic phenomena involving nonplanar motions of the ropes, impact loads between the ropes and the shaft walls, as well as vertical vibrations of the car, counterweight and compensating sheave. Such an adverse dynamic behaviour of the system endangers the safety of the installation. This paper presents two mathematical models describing the nonlinear responses of a suspension/ compensating rope system coupled with the elevator car / compensating sheave motions. The models accommodate the nonlinear couplings between the lateral and longitudinal modes, with and without longitudinal inertia of the ropes. The partial differential nonlinear equations of motion are derived using Hamilton Principle. Then, the Galerkin method is used to discretise the equations of motion and to develop a nonlinear ordinary differential equation model. Approximate numerical solutions are determined and the behaviour of the system is analysed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Analytic derivative couplings in time-dependent density functional theory: Quadratic response theory versus pseudo-wavefunction approach

We revisit the formalism for analytic derivative couplings between excited states in time-dependent density functional theory (TDDFT). We derive and implement these couplings using quadratic response theory, then numerically compare this response-theory formulation to couplings implemented previously based on a pseudo-wavefunction formalism and direct differentiation of the Kohn-Sham determinant. Numerical results, including comparison to full configuration interaction calculations, suggest that the two approaches perform equally well for many molecular systems, provided that the underlying DFT method affords accurate potential energy surfaces. The response contributions are found to be important for certain systems with high symmetry, but can be calculated with only a moderate increase in computational cost beyond what is required for the pseudo-wavefunction approach. In the case of spin-flip TDDFT, we provide a formal proof that the derivative couplings obtained using response theory are identical to those obtained from the pseudo-wavefunction formulation, which validates our previous implementation based on the latter formalism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗