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Results for “molecular electronics”

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.

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At least 1,081 records · Page 60
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Switching the conductance of a single molecule: Lessons from molecular junctions

The concept of using single molecules as functional building blocks in electronic circuitry represents the ultimate device miniaturization and has garnered tremendous attention from physics, chemistry, and engineering. Recent advances in single-molecule junction techniques have enabled direct investigation of charge transport in a quasi-one-dimensional conduction channel composed of an individual molecule. Furthermore, one of the main research focuses over the past decade has been to understand the conductance switching effect of single molecules as it is essential for developing molecular-scale optoelectronics, computing, and sensing applications. In this perspective, we highlight the established physical and chemical mechanisms for single-molecule conductance switching behavior and examine the associated stimuli in single-molecule junction systems.

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

A molecular dynamics study of laser-excited gold

The structural evolution of laser-excited systems of gold has previously been measured through ultrafast MeV electron diffraction. However, there has been a long-standing inability of atomistic simulations to provide a consistent picture of the melting process, leading to large discrepancies between the predicted threshold energy density for complete melting, as well as the transition between heterogeneous and homogeneous melting. We make use of two-temperature classical molecular dynamics simulations utilizing three highly successful interatomic potentials and reproduce electron diffraction data presented by Mo et al. [Science 360, 1451–1455 (2018)]. We recreate the experimental electron diffraction data, employing both a constant and temperature-dependent electron–ion equilibration rate. In all cases, we are able to match time-resolved electron diffraction data, and find consistency between atomistic simulations and experiments, only by allowing laser energy to be transported away from the interaction region. This additional energy-loss pathway, which scales strongly with laser fluence, we attribute to hot electrons leaving the target on a timescale commensurate with melting.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Spatially resolved density measurements of singlet delta oxygen in a non-equilibrium atmospheric pressure plasma jet by molecular beam mass spectrometry

Singlet delta oxygen (O 2 (a 1 Δ g )), the first electronically excited state of O 2 , plays an important role in many applications. We report the first measurements of absolute densities of O 2 (a 1 Δ g ) in an atmospheric pressure plasma jet (APPJ) by molecular beam mass spectrometry (MBMS). The ability to measure axial and radial profiles of O 2 (a 1 Δ g ) impinging on a substrate in the effluent of the APPJ is a key advantage of the MBMS diagnostic method over previously reported optical methods. Here, the measured large O 2 (a 1 Δ g ) densities in the APPJ effluent, up to one order of magnitude higher than the O density, underline the potential importance of O 2 (a 1 Δ g ) in many applications using APPJs.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Molecular beam homoepitaxy of N-polar AlN: Enabling role of aluminum-assisted surface cleaning

N-polar aluminum nitride (AlN) is an important building block for next-generation high-power radio frequency electronics. We report successful homoepitaxial growth of N-polar AlN by molecular beam epitaxy (MBE) on large-area, cost-effective N-polar AlN templates. Direct growth without any in situ surface cleaning leads to films with inverted Al polarity. It is found that Al-assisted cleaning before growth enables the epitaxial film to maintain N-polarity. The grown N-polar AlN epilayer with its smooth, pit-free surface duplicates the structural quality of the substrate, as evidenced by a clean and smooth growth interface with no noticeable extended defects generation. Near band-edge photoluminescence peaks are observed at room temperature on samples with MBE-grown layers but not on the bare AlN templates, implying the suppression of nonradiative recombination centers in the epitaxial N-polar AlN.

42 ENGINEERING↗
DOE OSTI2024

Electron transfer in a crystalline cytochrome with four hemes

Diffusion of electrons over distances on the order of 100 μm has been observed in crystals of a small tetraheme cytochrome (STC) from Shewanella oneidensis [J. Huang et al . J. Am. Chem. Soc. 142, 10459–10467 (2020)]. Electron transfer between hemes in adjacent subunits of the crystal is slower and more strongly dependent on temperature than had been expected based on semiclassical electron-transfer theory. Here, in this work, we explore explanations for these findings by molecular-dynamics simulations of crystalline and monomeric STC. New procedures are developed for including time-dependent quantum mechanical energy differences in the gap between the energies of the reactant and product states and for evaluating fluctuations of the electronic-interaction matrix element that couples the two hemes. Rate constants for electron transfer are calculated from the time- and temperature-dependent energy gaps, coupling factors, and Franck–Condon-weighted densities of states using an expression with no freely adjustable parameters. Back reactions are considered, as are the effects of various protonation states of the carboxyl groups on the heme side chains. Interactions with water are found to dominate the fluctuations of the energy gap between the reactant and product states. The calculated rate constant for electron transfer from heme IV to heme Ib in a neighboring subunit at 300 K agrees well with the measured value. However, the calculated activation energy of the reaction in the crystal is considerably smaller than observed. We suggest two possible explanations for this discrepancy. The calculated rate constant for transfer from heme I to II within the same subunit of the crystal is about one-third that for monomeric STC in solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Electron hopping heat transport in molecules

The realization of single-molecule thermal conductance measurements has driven the need for theoretical tools to describe conduction processes that occur over atomistic length scales. In macroscale systems, the principle that is typically used to understand thermal conductivity is Fourier’s law. At molecular length scales, however, deviations from Fourier’s law are common in part because microscale thermal transport properties typically depend on the complex interplay between multiple heat conduction mechanisms. Here, the thermal transport properties that arise from electron transfer across a thermal gradient in a molecular conduction junction are examined theoretically. We illustrate how transport in a model junction is affected by varying the electronic structure and length of the molecular bridge in the junction as well as the strength of the coupling between the bridge and its surrounding environment. Three findings are of note: First, the transport properties can vary significantly depending on the characteristics of the molecular bridge and its environment; second, the system’s thermal conductance commonly deviates from Fourier’s law; and third, in properly engineered systems, the magnitude of electron hopping thermal conductance is similar to what has been measured in single-molecule devices.

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

Tuning Conjugated Polymer Chain Packing for Stretchable Semiconductors

We report in order to apply polymer semiconductors to stretchable electronics, they need to be easily deformed under strain without being damaged. A small number of conjugated polymers, typically with semicrystalline packing structures, have been reported to exhibit mechanical stretchability. Herein, a method is reported to modify polymer semiconductor packing-structure using a molecular additive, dioctyl phthalate (DOP), which is found to act as a molecular spacer, to be inserted between the amorphous chain networks and disrupt the crystalline packing. As a result, large-crystal growth is suppressed while short-range aggregations of conjugated polymers are promoted, which leads to an improved mechanical stretchability without affecting charge-carrier transport. Due to the reduced conjugated polymer intermolecular interactions, strain-induced chain alignment and crystallization are observed. By adding DOP to a well-known conjugated polymer, poly[2,5-bis(4-decyltetradecyl)pyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione-(E)-1,2-di(2,2 '-bithiophen-5-yl)ethene] (DPPTVT), stretchable transistors are obtained with anisotropic charge-carrier mobilities under strain, and stable current output under strain up to 100%.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Redox active plant phenolic, acetosyringone, for electrogenetic signaling

Abstract Redox is a unique, programmable modality capable of bridging communication between biology and electronics. Previous studies have shown that the E. coli redox-responsive OxyRS regulon can be re-wired to accept electrochemically generated hydrogen peroxide (H 2 O 2 ) as an inducer of gene expression. Here we report that the redox-active phenolic plant signaling molecule acetosyringone (AS) can also induce gene expression from the OxyRS regulon. AS must be oxidized, however, as the reduced state present under normal conditions cannot induce gene expression. Thus, AS serves as a “pro-signaling molecule” that can be activated by its oxidation—in our case by application of oxidizing potential to an electrode. We show that the OxyRS regulon is not induced electrochemically if the imposed electrode potential is in the mid-physiological range. Electronically sliding the applied potential to either oxidative or reductive extremes induces this regulon but through different mechanisms: reduction of O 2 to form H 2 O 2 or oxidation of AS. Fundamentally, this work reinforces the emerging concept that redox signaling depends more on molecular activities than molecular structure. From an applications perspective, the creation of an electronically programmed “pro-signal” dramatically expands the toolbox for electronic control of biological responses in microbes, including in complex environments, cell-based materials, and biomanufacturing.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

In search of molecular ions for optical cycling: a difficult road

Optical cycling, a continuous photon scattering off atoms or molecules, plays a central role in the quantum information science. While optical cycling has been experimentally achieved for many neutral species, few molecular ions have been investigated. We present a systematic theoretical search for diatomic molecular ions suitable for optical cycling using equation-of-motion coupled-cluster methods. Inspired by the electronic structure patterns of laser-cooled neutral molecules, we establish the design principles for molecular ions and explore various possible cationic molecular frameworks. The results show that finding a perfect molecular ion for optical cycling is challenging, yet possible. Among various possible diatomic molecules we suggest several candidates, which require further attention from both theory and experiment: YF + , SiO + , PN + , SiBr + , and BO + .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Reliable p K a Prediction through Efficient Incorporation of Anharmonicity within the Nuclear–Electronic Orbital Framework

Accurate pK a prediction is critical for understanding chemical reactivity and molecular properties across a wide range of applications. Computational approaches usually invoke a harmonic treatment of the vibrational modes for zero-point energies, as well as thermal and entropic contributions. Herein, we present a general protocol for relative pK a prediction that incorporates the significant anharmonic effects using nuclear–electronic orbital (NEO) theory. This protocol is validated against experimental data for a range of molecules in acetonitrile, including protonated nitrogen bases, nitrophenols, anilines, and diamines, as well as cobalt electrocatalysts. For simple acids, the NEO approach offers only a slight improvement over conventional density functional theory with the standard harmonic vibrational treatment, whereas for hydrogen-bonded acids, the NEO approach offers more significantly improved performance at a comparable computational cost. This accessible methodology provides a practical route for accurate pKa prediction in challenging systems and is extendable to related thermodynamic properties such as hydricities and proton-coupled redox potentials.

Density functional theory↗
DOE OSTI2024

Ligand Controls Excited Charge Carrier Dynamics in Metal-Rich CdSe Quantum Dots: Computational Insights

Small metal-rich semiconducting quantum dots (QDs) are promising for solid-state lighting and single-photon emission due to their highly tunable yet narrow emission line widths. Nonetheless, the anionic ligands commonly employed to passivate these QDs exert a substantial influence on the optoelectronic characteristics, primarily owing to strong electron–phonon interactions. In this work, we combine time-domain density functional theory and nonadiabatic molecular dynamics to investigate the excited charge carrier dynamics of Cd 28 Se 17 X 22 QDs (X = HCOO – , OH – , Cl – , and SH – ) at ambient conditions. These chemically distinct but regularly used molecular groups influence the dynamic surface-ligand interfacial interactions in Cd-rich QDs, drastically modifying their vibrational characteristics. The strong electron–phonon coupling leads to substantial transient variations at the band edge states. The strength of these interactions closely depends on the physicochemical characteristics of passivating ligands. Consequently, the ligands largely control the nonradiative recombination rates and emission characteristics in these QDs. Our simulations indicate that Cd 28 Se 17 (OH) 22 has the fastest nonradiative recombination rate due to the strongest electron–phonon interactions. Conversely, QDs passivated with thiolate or chloride exhibit considerably longer carrier lifetimes and suppressed nonradiative processes. The ligand-controlled electron–phonon interactions further give rise to the broadest and narrowest intrinsic optical line widths for OH and Cl-passivated single QDs, respectively. Finally, obtained computational insights lay the groundwork for designing appropriate passivating ligands on metal-rich QDs, making them suitable for a wide range of applications, from blue LEDs to quantum emitters.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Neuromorphic heat transport effects in a molecular junction

Understanding energy transport at the nanoscale is an open and fundamental challenge in the molecular sciences with direct implications for the design of new electronics, computing devices, and materials. While nanoscale energy transport under steady-state conditions has been studied extensively, there is much less known about energy transport under time-dependent driving forces, particularly in the far-from-equilibrium regime. In this work, we use nonequilibrium molecular dynamics simulations and stochastic thermodynamics to investigate energy transport in a well-studied nanoscale system—a molecular junction—subjected to a time-periodic temperature gradient. The primary observation is that molecular junctions can exhibit heat transport hysteresis, a phenomenon in which the heat flux through a system depends not only on the instantaneous value of a time-dependent temperature bias but also on the temporal history of that bias. The presented findings illustrate that molecular junctions can exhibit the specific memory effect—heat transport hysteresis—that is essential for the design of thermal neuromorphic computers. This work elucidates a potential pathway toward the realization of such devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Frontiers in divalent $f$-block chemistry

Divalent f-block chemistry has undergone rapid expansion in recent years, driven by advances in the stabilization of low-valent lanthanide and actinide complexes. Although f-elements were historically accessed in the +3 or higher oxidation states, the isolation of +2 species has revealed unusual spectroscopic signatures, distinct bonding motifs, and multiple accessible electronic configurations that influence their chemical and physical properties. These developments have generated opportunities in areas including quantum information science, molecular magnetism, catalysis, and luminescence. Computational chemistry has played a pivotal role in interpreting the electronic structure and reactivity of these systems. However, accurately modeling divalent f-block complexes remains challenging because of strong electronic correlation, multiconfigurational character, and the presence of close-in-energy competing electronic states. As experimental capabilities and theoretical methodologies continue to advance, a comprehensive assessment of divalent chemistry is both timely and needed. In this Review, we integrate experimental and theoretical perspectives to provide a systematic analysis of divalent lanthanide and actinide complexes across the f-block series. We critically assess the role of ligands in determining competing ground-state configurations (f n d 1 vs. f n+1 ) resulting in their distinct spectroscopic, magnetic, and bonding properties. Finally, we discuss emerging strategies for predictive modeling and rational design of low-valent f-block molecular systems, with potential applications ranging from dinitrogen reduction to quantum technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Direct structural retrieval from gas-phase ultrafast diffraction data using a genetic algorithm

Ultrafast scattering techniques such as ultrafast electron diffraction and ultrafast x-ray diffraction have been utilized to elucidate the structural dynamics, reaction intermediates, and final products in molecular reactions following photoexcitation. The time-dependent structures are typically not directly retrieved from the experimental data, but they rely on comparison with calculations. The genetic algorithm (GA), a global optimization strategy, can be used to retrieve the molecular structures directly from diffraction patterns without any theoretical input. However, the robustness of the GA with respect to real experimental conditions such as a limited momentum transfer range, noise, and artifacts has not been studied in detail. In this work, we characterize the performance of the GA with simulated data that mimic realistic experimental conditions. We have developed and implemented a variant of the GA specific to diffraction measurements which performs better in the presence of imperfect data compared to the standard implementation of the GA. We demonstrate this method with both synthetic data and experimental ultrafast electron diffraction data on the UV-induced photodissociation of trifluoroiodomethane (C⁢F 3⁡ I) molecules.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Revealing hidden defects through stored energy measurements of radiation damage

With full knowledge of a material’s atomistic structure, it is possible to predict any macroscopic property of interest. In practice, this is hindered by limitations of the chosen characterization techniques. For example, electron microscopy is unable to detect the smallest and most numerous defects in irradiated materials. Instead of spatial characterization, we propose to detect and quantify defects through their excess energy. Differential scanning calorimetry of irradiated Ti measures defect densities five times greater than those determined using transmission electron microscopy. Our experiments also reveal two energetically distinct processes where the established annealing model predicts one. Molecular dynamics simulations discover the defects responsible and inform a new mechanism for the recovery of irradiation-induced defects. The combination of annealing experiments and simulations can reveal defects hidden to other characterization techniques and has the potential to uncover new mechanisms behind the evolution of defects in materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Probing Molecular Assembly of Small Organic Molecules during Meniscus-Guided Coating Using Experimental and Molecular Dynamics Approaches

Evaporation-based thin-film coating processes are ubiquitous in fields such as organic electronics, dye coatings, and the pharmaceutical industry. Based on experimental observations of enhanced thin-film alignment during meniscus-guided coating (MGC), a molecular dynamics simulation was developed to describe the thin-film formation that occurs due to the interplay between evaporation and fluid dynamics. The process of solvent evaporation from solution is first examined, which leads to the formation of a solid thin film after evaporation is complete. Next, an MGC process was simulated by introducing a flow profile coupled with the evaporative system. In this work, we gain insights into how molecules respond and reorient in the presence of a flow profile. These results indicate that both the evaporation and the flow profile have an impact on orienting small molecules in a thin film during the MCG process. Combining experimental techniques with simulations helps enhance the understanding of the forces that are significant in directing molecular aggregation during coating processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Structural and electronic characteristics of amorphous Ge 8 Sb 2 Te 11

GeTe-rich phase-change materials can be utilized in rewriteable optical memory due to the large contrast in reflectivity between amorphous and crystalline phases. Here we explored the structure and electronic properties of amorphous Ge 8 Sb 2 Te 11 using ab initio molecular dynamics simulations. The results indicate that amorphous Ge 8 Sb 2 Te 11 is dominantly composed of Ge-, Sb- and Te-centered octahedrons with distortions, while 30.4 % of Ge-centered clusters are in the form of tetrahedrons which are randomly distributed. The 5-fold rings possess a large proportion, and the Gesingle bondTe and Sbsingle bondTe bonds present larger formation energies than other bonds, leading to the ABAB bonding sequence (A: Ge and Sb, B: Te). The lone pair electrons locating at the opposite direction of bonds possess a large fraction of 14.8 %, which may enhance the distortions of local clusters. Importantly, these structural properties lead to the high stability of amorphous Ge 8 Sb 2 Te 11 and thus long data retention in the information storage.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Dynamic Molecular Investigation of the Solid-Electrolyte Interphase of an Anode-Free Lithium Metal Battery Using In Situ Liquid SIMS and Cryo-TEM

Solid electrolyte interphase (SEI) has been widely perceived to play a critical role in the stable cycling of rechargeable batteries. However, associated with the fragile and air-sensitive nature of the SEI layer, delineation of the formation process and the nature of SEI remains a big challenge. Here, we use in situ liquid time-of-flight secondary ion mass spectroscopy (TOF-SIMS), cryo- transmission electron microscope (TEM) and density functional theory (DFT) calculation to delineate molecular process on the formation of SEI layer under the dynamic operating condition. We discover that the onset potential for SEI layer formation and the thickness of the SEI show dependence on the solvation shell structure. Using LiCoO 2 as a cathode and Cu film as an anode, the SEI is noticed to start to form at around 2.0 V and reach its final thickness (irreversible part, ~ 40-50 nm) at about 3.0 V in the 1 M LiPF 6 –EC/DMC electrolyte, while for the case of 1 M LiFSI–DME, the SEI starts to form at around 1.5 V and reaches its final thickness (~ 20 nm) at about 2.0 V. The in situ TOF-SIMS clearly indicates the outer SEI layer formation and dissipation upon charging and discharging, implying a continued evolution of electrolyte structure with extended cycling. In conclusion, the present work establishes a direct correlation between the molecular signature of SEI layer with solvation feature of electrolytes in lithium batteries, providing insights for tailoring SEI layer toward improved electrochemical properties of lithium batteries.

25 ENERGY STORAGE↗