SEARCH · Engineering Papers

Results for “coupling constant”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 379 records · Page 21

All sources NASA NTRS DOE OSTI

DOE OSTI2020

The well-tempered cosmological constant: the Horndeski variations

Well tempering is one of the few classical field theory methods for solving the original cosmological constant problem, dynamically canceling a large (possibly Planck scale) vacuum energy and leaving the matter component intact, while providing a viable cosmology with late time cosmic acceleration and an end de Sitter state. We present the general constraints that variations of Horndeski gravity models with different combinations of terms must satisfy to admit an exact de Sitter spacetime that does not respond to an arbitrarily large cosmological constant. We explicitly derive several specific scalar-tensor models that well temper and can deliver a standard cosmic history including current cosmic acceleration. Stability criteria, attractor behavior of the de Sitter state, and the response of the models to pressureless matter are considered. The well tempered conditions can be used to focus on particular models of modified gravity that have special interest— not only removing the original cosmological constant problem but providing relations between the free Horndeski functions and reducing them to a couple of parameters, suitable for testing gravity and cosmological data analysis.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2022

Quantification of electrochemical-mechanical coupling in lithium-ion batteries

Lithium-ion battery safety and durability by nature are dependent on electrochemical and mechanical coupling. Interdisciplinary efforts are required to understand and quantify coupling behaviors. Here we design and conduct mechanically constrained charge and discharge characterizations with efforts supported by multiphysics modeling to unravel the coupling mechanisms of solid-liquid electrode-electrolyte and solid-solid active materials in lithium-ion batteries. We demonstrate that a lithium-ion battery cell under mechanical constraint exhibits a higher voltage during charging and a shorter charging time because of increased electrolyte resistance and decreased diffusivity caused by decreased electrode porosity. The reaction force response of the cell is a combined result of the cell structural response mechanically and lithium-ion intercalation/de-intercalation-induced volume variation electrochemically. Under mechanical constraint, cell capacity is significantly reduced in fast-charge scenarios; however, it can be recovered by a constant-voltage charge protocol. The results highlight the promise of multiphysics approaches to unravel the electrochemical-mechanical coupling mechanisms to direct battery system design and management.

25 ENERGY STORAGE↗

DOE OSTI2022

Optimizing Piezoelectric Nanocomposites by High‐Throughput Phase‐Field Simulation and Machine Learning

Abstract Piezoelectric nanocomposites with oxide fillers in a polymer matrix combine the merit of high piezoelectric response of the oxides and flexibility as well as biocompatibility of the polymers. Understanding the role of the choice of materials and the filler‐matrix architecture is critical to achieving desired functionality of a composite towards applications in flexible electronics and energy harvest devices. Herein, a high‐throughput phase‐field simulation is conducted to systematically reveal the influence of morphology and spatial orientation of an oxide filler on the piezoelectric, mechanical, and dielectric properties of the piezoelectric nanocomposites. It is discovered that with a constant filler volume fraction, a composite composed of vertical pillars exhibits superior piezoelectric response and electromechanical coupling coefficient as compared to the other geometric configurations. An analytical regression is established from a linear regression‐based machine learning model, which can be employed to predict the performance of nanocomposites filled with oxides with a given set of piezoelectric coefficient, dielectric permittivity, and stiffness. This work not only sheds light on the fundamental mechanism of piezoelectric nanocomposites, but also offers a promising material design strategy for developing high‐performance polymer/inorganic oxide composite‐based wearable electronics.

42 ENGINEERING↗

DOE OSTI2020

Partitioned exponential methods for coupled multiphysics systems

Multiphysics problems involving two or more coupled physical phenomena are ubiquitous in science and engineering. This work develops a new partitioned exponential approach for the time integration of multiphysics problems. After a possible semi-discretization in space, the class of problems under consideration is modeled by a system of ordinary differential equations where the right-hand side is a summation of two component functions, each corresponding to a given set of physical processes. The partitioned-exponential methods proposed herein evolve each component of the system via an exponential integrator, and information between partitions is exchanged via coupling terms. Here, the traditional approach to constructing exponential methods, based on the variation-of-constants formula, is not directly applicable to partitioned systems. Rather, our approach to developing new partitioned-exponential families is based on a general-structure additive formulation of the schemes. Two method formulations are considered, one based on a linear-nonlinear splitting of the right hand component functions, and another based on approximate Jacobians. The paper develops classical (non-stiff) order conditions theory for partitioned exponential schemes based on particular families of T-trees and B-series theory. Several practical methods of third order are constructed that extend the Rosenbrock-type and EPIRK families of exponential integrators. Several implementation optimizations specific to the application of these methods to reaction-diffusion systems are also discussed. Numerical experiments reveal that the new partitioned-exponential methods can perform better than traditional unpartitioned exponential methods on some problems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2025

Exceptional points in a passive strip waveguide

Abstract Exceptional points (EPs) in non‐Hermitian systems have attracted significant interest due to their unique behaviors, including novel wave propagation and radiation. While EPs have been explored in various photonic systems, their integration into standard photonic platforms can expand their applicability to broader technological domains. In this work, we propose and experimentally demonstrate EPs in an integrated photonic strip waveguide configuration, exhibiting unique deep wave penetration and uniform‐intensity radiation profiles. By introducing the second‐order grating on one side of the waveguide, forward and backward propagating modes are coupled both directly through second‐order coupling and indirectly through first‐order coupling via a radiative intermediate mode. To describe the EP behavior in a strip configuration, we introduce modified coupled‐mode equations that account for both transverse and longitudinal components. These coupled‐mode formulas reveal the formation of EPs in bandgap closure, achieved by numerically optimizing the grating’s duty cycle to manipulate the first‐ and second‐order couplings simultaneously. Experimental observations, consistent with simulations, confirm the EP behavior, with symmetric transmission spectra and constant radiation profiles at the EP wavelength, in contrast to conventional exponential decay observed at detuned wavelengths. These results demonstrate the realization of EPs in a widely applicable strip waveguide configuration, paving the way for advanced EP applications in nonlinear and ultrafast photonics, as well as advanced sensing technologies.

Materials Science↗

DOE OSTI2022

A physics-based model of cladding wastage layer formation rate

In this report, lower length scale simulations to inform an engineering-scale model of fuel-cladding chemical interaction (FCCI) conducted under the auspices of the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program in FY22 are described. An overall strategy for the implementation of the BISON model is described, and the past and current lower length scale work on FCCI formation is put into the context of this overall strategy. Density functional theory and kinetic Monte Carlo simulations are used to determine the diffusion coefficient of neodymium in iron. Density functional theory calculations are also used to parameterize a parabolic approximation for the dependence of free energy on composition for the intermetallic compound Fe 17 Nd 2 . A phase-field model of the Fe-Nd system was developed that includes the random solid solution body-centered cubic phase and the intermetallic Fe 17 Nd 2 . The model was used to simulate growth of the intermetallic layer in a diffusion couple and the results were compared to experiment. The model’s prediction of the parabolic growth constant is within 40 % of the experimental value. The model is also used to simulate the formation of a grain boundary attack layer that is observed in experiment. The simulations show enhanced Nd concentration along the grain boundaries, but do not clearly show formation of a Fe 17 Nd 2 layer

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2021

Proton-detected 15 N- 1 H dipolar coupling/ 1 H chemical shift correlation experiment for the measurement of NH distances in biological solids under fast MAS solid-state NMR

Measurement of distances from dipolar couplings is essential for structural characterization, refinement and validation using the solid-state nuclear magnetic resonance (ssNMR) spectroscopy. Particularly, knowledge about NH dipolar interactions in biological solids is important for understanding the hydrogen (H)-bonding interactions, molecular geometry and spin dynamics. In this regard, we have proposed a proton-detected two-dimensional (2D) 15 N- 1 H dipolar coupling/ 1 H chemical shift correlation experiment using the C-symmetry based windowless recoupling of chemical shift anisotropy (ROCSA) in combination with the DIPSHIFT pulse-based method for the measurement of short NH distances in the isotopically labeled and naturally abundant biological solids at fast magic angle spinning (MAS) rates (40–70 kHz). Our proposed method results in undistorted recoupled 15 N- 1 H dipolar coupling powder lineshapes that are free from the recoupled 1 H CSA contributions under the 15 N evolution, a feature that is essential for the measurement of NH distances with improved accuracy (± 500 Hz in terms of the NH dipolar couplings). The pulse sequence developed in the present study is also insensitive to the 1H–1H homonuclear dipolar interactions, relaxation effects owing to its constant-time implementation, and t1-noise from the fluctuations in the MAS.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2023

Quantum dynamical effects of vibrational strong coupling in chemical reactivity

Abstract Recent experiments suggest that ground state chemical reactivity can be modified when placing molecular systems inside infrared cavities where molecular vibrations are strongly coupled to electromagnetic radiation. This phenomenon lacks a firm theoretical explanation. Here, we employ an exact quantum dynamics approach to investigate a model of cavity-modified chemical reactions in the condensed phase. The model contains the coupling of the reaction coordinate to a generic solvent, cavity coupling to either the reaction coordinate or a non-reactive mode, and the coupling of the cavity to lossy modes. Thus, many of the most important features needed for realistic modeling of the cavity modification of chemical reactions are included. We find that when a molecule is coupled to an optical cavity it is essential to treat the problem quantum mechanically to obtain a quantitative account of alterations to reactivity. We find sizable and sharp changes in the rate constant that are associated with quantum mechanical state splittings and resonances. The features that emerge from our simulations are closer to those observed in experiments than are previous calculations, even for realistically small values of coupling and cavity loss. This work highlights the importance of a fully quantum treatment of vibrational polariton chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

New-Generation Carbon-Capture Ionic Liquids Regulated by Metal-Ion Coordination

Development of efficient carbon capture-and-release technologies with minimal energy input is a long-term challenge in mitigating CO 2 emissions, especially via CO 2 chemisorption driven by engineered chemical bond construction. Herein, taking advantage of the structural diversity of ionic liquids (ILs) in tuning their physical and chemical properties, precise reaction energy regulation of CO 2 chemisorption was demonstrated deploying metal-ion-amino-based ionic liquids (MAILs) as absorbents. The coordination ability of different metal sites (Cu, Zn, Co, Ni, and Mg) to amines was harnessed to achieve fine-tuning on stability constants of the metal ion-amine complexes, acting as the corresponding cations in the construction of diverse ILs coupled with CO 2 -philic anions. The as-afforded MAILs exhibited efficient and controllable CO 2 release behavior with great reduction in energy input and minimal sacrifice on CO 2 uptake capacity. This coordination-regulated approach offers new prospects for the development of ILs-based systems and beyond towards energy-efficient carbon capture technologies.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Solvothermal Synthesis of [Cr 7 S 8 (en) 8 Cl 2 ]Cl 3 ⋅ 2H 2 O with Magnetically Frustrated [Cr 7 S 8 ] 5+ Double‐Cubes**

Abstract A novel transition metal chalcohalide [Cr 7 S 8 (en) 8 Cl 2 ]Cl 3 ⋅ 2H 2 O, with [Cr 7 S 8 ] 5+ dicubane cationic clusters, has been synthesized by a low temperature solvothermal method, using dimethyl sulfoxide (DMSO) and ethylenediamine ( en ) solvents. Ethylenediamine ligand exhibits bi‐ and monodentate coordination modes; in the latter case ethylenediamine coordinates to Cr atoms of adjacent clusters, giving rise to a 2D polymeric structure. Although magnetic susceptibility shows no magnetic ordering down to 1.8 K, a highly negative Weiss constant, θ =−224(2) K, obtained from Curie‐Weiss fit of inverse susceptibility, suggests strong antiferromagnetic (AFM) interactions between S =3/2 Cr(III) centers. Due to the complexity of the system with (2 S +1) 7 =16384 microstates from seven Cr 3+ centers, a simplified model with only two exchange constants was used for simulations. Density‐functional theory (DFT) calculations yielded the two exchange constants to be J 1 =−21.4 cm −1 and J 2 =−30.2 cm −1 , confirming competing AFM coupling between the shared Cr 3+ center and the peripheral Cr 3+ ions of the dicubane cluster. The best simulation of the experimental data was obtained with J 1 =−20.0 cm −1 and J 2 =−21.0 cm −1 , in agreement with the slightly stronger AFM exchange within the triangles of the peripheral Cr 3+ ions as compared to the AFM exchange between the central and peripheral Cr 3+ ions. This compound is proposed as a synthon towards magnetically frustrated systems assembled by linking dicubane transition metal‐chalcogenide clusters into polymeric networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

R -parity violation axiogenesis

We show that the rotation of the QCD axion field, aided by B–L violation from supersymmetric R-parity violating couplings, can yield the observed baryon abundance. Strong sphaleron processes transfer the angular momentum of the axion field into a quark chiral asymmetry, which R-parity violating couplings convert to the baryon asymmetry of the Universe. We focus on the case of dimensionless R-parity violating couplings with textures motivated by grand unified theories and comment on more general scenarios. The axion decay constant and mass spectrum of supersymmetric particles are constrained by Big Bang nucleosynthesis, proton decay from the R-parity violation, and successful thermalization of the Peccei-Quinn symmetry breaking field. Axion dark matter may be produced by the axion rotation via the kinetic misalignment mechanism for axion decay constants below 10 10 GeV, or by the conventional misalignment mechanism for 10 11-12 GeV. The viable parameter region can be probed by proton decay and axion searches. This scenario may also have connections with collider experiments, including searches for long-lived particles, and observations of gravitational waves.

Beyond Standard Model↗

DOE OSTI2026

Enhanced coercivity in Fe5C2/SiO2 core/shell nanocrystals

Rod-shaped Fe5C2 and core/shell Fe5C2/SiO2 nanocrystals were synthesized via a solution-based chemical method. Structural analysis confirmed the monoclinic phase of Fe5C2 with space group C2/c. Zero-field-cooling (ZFC) and field-cooling (FC) magnetization curves revealed distinct magnetic behaviors: uncoated Fe5C2 exhibited a low-temperature FC plateau indicative of strong dipolar interactions, while Fe5C2/SiO2 showed a monotonic increase in FC magnetization, suggesting reduced dipolar interactions due to SiO2 surface passivation. Isothermal remanent magnetization (IRM) and DC demagnetization (DCD) measurements supported this trend, with δM plots confirming weaker dipolar interactions in the coated sample. Bloch’s law fitting of temperature-dependent saturation magnetization showed a smaller Bloch’s constant for pure Fe5C2 and a larger value for Fe5C2/SiO2, reflecting enhanced surface disorder and reduced exchange coupling in the latter. Notably, Fe5C2/SiO2 demonstrated increased coercivity, attributed to decreased dipolar interaction and elevated surface anisotropy. Kneller’s law fitting yielded higher blocking temperatures for Fe5C2 (476 K) than Fe5C2/SiO2 (456 K), highlighting the impact of dipolar interactions on magnetic relaxation. These findings illustrate how SiO2 coatings effectively modulate dipolar interactions and enhance coercivity in Fe5C2 nanocrystals.

Joshi, Pramanand [Department of Physics, Universit↗

DOE OSTI2021

Weak scale as a trigger

Does the value of the Higgs mass parameter affect the expectation value of local operators in the Standard Model? For essentially all local operators the answer to this question is "no", and this is one of the avatars of the hierarchy problem: nothing is "triggered" when the Higgs mass parameter crosses zero. In this letter, we explore settings in which Higgs mass parameters $can$ act as a "trigger" for some local operators ${\cal O}_T$. In the Standard Model, this happens for ${\cal O}_T = {\rm Tr} (G \tilde G)$. We also introduce a "type-0" two Higgs doublet model, with a $Z_4$ symmetry, for which ${\cal O}_T = H_1 H_2$ is triggered by the Higgs masses, demanding the existence of new Higgs states necessarily comparable to or lighter than the weak scale, with no wiggle room to decouple them whatsoever. Surprisingly, this model is not yet entirely excluded by collider searches, and will be incisively probed by the high-luminosity run of the LHC, as well as future Higgs factories. We also discuss a possibility for using this trigger to explain the origin of the weak scale, invoking a landscape of extremely light, weakly interacting scalars $\phi_i$, with a coupling to ${\cal O}_T$ needed to make it possible to find vacua with small enough cosmological constant. The weak scale trigger links the tuning of the Higgs mass to that of the cosmological constant, while coherent oscillations of the $\phi_i$ can constitute dark matter.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2024

Reconceptualizing the Ir III Role in Metallaphotoredox Catalysis: From Strong Photooxidant to Potent Energy Donor

Dual Ir III /L n Ni II metallaphotoredox catalyzed C(sp 3 )–C(sp 2 ) cross-coupling reactions are widely assumed to proceed by photoinduced single electron transfer steps due to the highly oxidizing Ir III * excited state (Ir III = [Ir(dF(CF 3 )ppy) 2 (dtbbpy)] + [PF 6 ] – ; dF(CF 3 )ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; L n = dtbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine). Using time-resolved absorption and emission spectroscopy, we reveal that energy transfer between Ir III * and various LnNi II precatalysts and intermediates with k q ≥ 10 8 M –1 s –1 also drives catalysis. Specifically, the excited states of L n Ni II dihalide precatalysts/organometallic intermediates accessible by energy transfer appear to drive bond homolysis, halogen radical elimination, and reductive elimination reactions that facilitate formation of cross-coupled products. Energy transfer dynamics consequently circumvent the need for photoinduced electron transfer, thereby extending substrate scopes to coupling partners that cannot be oxidized by Ir III *. Within a cross-electrophile coupling model reaction between 4-bromobenzotrifluoride and bromocyclohexane, energy transfer activates the L n Ni II precatalyst at early reaction times before nucleophilic reductants are present. In the absence of Ir III , direct excitation of L n Ni II (Br) 2 also activates the precatalyst to form a L n Ni II (Br)(Aryl) intermediate. To compare energy transfer and electron transfer kinetics, we determined rate constants for reductive quenching by Br – (k SET = 4.1 × 10 8 M –1 s –1 ) and for the subsequent electron transfer from reduced Ir III•– to L n Ni II (Br) 2 (k SET = 4.1 × 10 7 M –1 s –1 ) using Stern-Volmer analysis and pulse radiolysis, respectively. Energy transfer rate constants are competitive with the electron transfer rate constants and energy transfer is a parallel pathway within metallaphotoredox catalysis. Exploiting the energy transfer mechanism, we demonstrate highly selective cross-electrophile coupling between 4-chlorobenzotrifluoride and bromocyclohexane to form exclusively cross-coupled product. Here, with alkyl-trifluoroborate nucleophiles that do not reductively quench IrIII* emission, transmetalation with L n Ni II (Br/Cl)(Aryl) followed by energy transfer also drives excited state reductive elimination to form C(sp 3 )–C(sp 2 ) cross-coupled product. Similarly, energy transfer rather than Ni II oxidation drives C(sp 2 )–OR reductive elimination, despite the strongly oxidizing ability of Ir III *. In total, these reactions demonstrate energy transfer processes from Ir III * to L n Ni II in metallaphotoredox catalysis that can unlock alternative reactive pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Extracting correlation effects from momentum-resolved electron energy loss spectroscopy: Synergistic origin of the dispersion kink in Bi 2.1 Sr 1.9 CaCu 2 O 8 + x

We employ momentum-resolved electron energy loss spectroscopy (M-EELS) on Bi 2.1 Sr 1.9 CaCu 2 O 8 + x to resolve the issue of the kink feature in the electron dispersion widely observed in the cuprates. To this end, we utilize the GW approximation to relate the density response function measured in M-EELS to the self-energy, isolating contributions from phonons, electrons, and the momentum dependence of the effective interaction to the decay rates. The phononic contributions, present in the M-EELS spectra due to electron-phonon coupling, lead to kink features in the corresponding single-particle spectra at energies between 40 and 80 meV, independent of the doping level. We find that a repulsive interaction constant in momentum space is able to yield the kink attributed to phonons in ARPES. Hence, our analysis of the M-EELS spectra points to local repulsive interactions as a factor that enhances the spectroscopic signatures of electron-phonon coupling in cuprates. We conclude that the strength of the kink feature in cuprates is determined by the combined action of electron-phonon coupling and electron-electron interactions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2023

Hybrid renewable energy systems: the value of storage as a function of PV-wind variability

As shares of variable renewable energy (VRE) on the electric grid increase, sources of grid flexibility will become increasingly important for maintaining the reliability and affordability of electricity supply. Lithium-ion battery energy storage has been identified as an important and cost-effective source of flexibility, both by itself and when coupled with VRE technologies like solar photovoltaics (PV) and wind. In this study, we explored the current and future value of utility-scale hybrid energy systems comprising PV, wind, and lithium-ion battery technologies (PV-wind-battery systems). Using a price-taker model with simulated hourly energy and capacity prices, we simulated the revenue-maximizing dispatch of a range of PV-wind-battery configurations across Texas, from the present through 2050. Holding PV capacity and point-of-interconnection capacity constant, we modeled configurations with varying wind-to-PV capacity ratios and battery-to-PV capacity ratios. We found that coupling PV, wind, and battery technologies allows for more effective utilization of interconnection capacity by increasing capacity factors to 60%–80%+ and capacity credits to close to 100%, depending on battery capacity. We also compared the energy and capacity values of PV-wind and PV-wind-battery systems to the corresponding stability coefficient metric, which describes the location-and configuration-specific complementarity of PV and wind resources. Our results show that the stability coefficient effectively predicts the configuration-location combinations in which a smaller battery component can provide comparable economic performance in a PV-wind-battery system (compared to a PV-battery system). These PV-wind-battery hybrids can help integrate more VRE by providing smoother, more predictable generation and greater flexibility.

14 SOLAR ENERGY↗

DOE OSTI2022

Large change of interlayer vibrational coupling with stacking in Mo 1-x W x Te 2

Stacking variations in quasi-two-dimensional materials can have an important influence on material properties, such as changing the topology of the band structure. Unfortunately, the weakness of van der Waals (vdW) interactions makes it difficult to compute the stacking dependence of properties, and even in a material as simple as graphite the stacking energetics remain unclear. Mo 1 - x W x Te 2 is a material in which three differently stacked phases are conveniently accessible by temperature changes: 1 T ' , T d * , and the reported Weyl semimetal phase T d . Additionally, the transitions proceed via layer sliding, and the corresponding interlayer shear mode (ISM) is relevant not just for the stacking energetics but also for understanding the relationship between Weyl physics and structural changes. However, the interlayer interactions of Mo 1 - x W x Te 2 are not well understood, with wide variation in computed properties. We report inelastic neutron scattering of the ISM in a Mo 0.91 W 0.09 Te 2 crystal. The ISM energies are generally consistent with the linear chain model, as expected given the weak interlayer interaction, though there are some discrepancies from predicted intensities. However, the interlayer force constants K x in the T d * and 1 T ' phases are substantially weaker than that of T d at 75(3) and 83(3)%, respectively. Considering that the relative positioning of atoms in neighboring layers is approximately the same regardless of overall stacking, our results suggest that longer-range influences, such as stacking-induced electronic band-structure changes, may be responsible for the substantial change in the interlayer vibrational coupling and thus the C 55 elastic constant. These findings should elucidate the stacking energetics of Mo 1 - x W x Te 2 and other vdW layered materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2020

Photoinduced charge transfer in Zn(II) and Au(III)-ligated symmetric and asymmetric bacteriochlorin dyads: A computational study

The excited-state properties and photoinduced charge-transfer (CT) kinetics in a series of symmetrical and asymmetrical Zn- and Au-ligated meso–meso-connected bacteriochlorin (BChl) complexes are studied computationally. BChl derivatives, which are excellent near-IR absorbing chromophores, are found to play a central role in bacterial photosynthetic reaction centers but are rarely used in artificial solar energy harvesting systems. The optical properties of chemically linked BChl complexes can be tuned by varying the linking group and involving different ligated metal ions. We investigate charge transfer in BChl dyads that are either directly linked or through a phenylene ring (1,4- phenylene) and which are ligating Zn or Au ions. The directly linked dyads with a nearly perpendicular arrangement of the BChl units bear markedly different properties than phenylene linked dyads. In addition, we find that the dielectric dependence of the intramolecular CT rate is very strong in neutral Zn-ligated dyads, whereas cationic Au-ligated dyads show negligible dielectric dependence of the CT rate. Rate constants of the photo induced CT process are calculated at the semiclassical Marcus level and are compared to fully quantum mechanical Fermi’s golden rule based values. The rates are calculated using a screened range separated hybrid functional that offers a consistent framework for addressing environment polarization. We study solvated systems in two solvents of a low and a high scalar dielectric constant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗