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At least 595 records · Page 33
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Molecular Recognition at Mineral Interfaces: Implications for the Beneficiation of Rare Earth Ores

Ce-bastnäsite is the single largest mineral source for light rare-earth elements. In view of the growing industrial importance of rare-earth minerals, it is critical to develop more efficient methods for separating the valuable rare-earth-containing minerals from the surrounding gangue. In this work, we employ a combination of periodic density functional theory (DFT) and molecular mechanics (MM) calculations together with the de novo molecular design program HostDesigner to identify bis-phosphinate ligands that preferentially bind to the (100) Ce-bastnäsite surface rather than the (104) calcite surface. DFT calculations for a simple phosphinate ligand were employed to qualitatively understand key behaviors involved in ligand–metal, ligand–solvent, and solvent–metal interactions. These insights were then used to guide the search for flexible, rigid, and semirigid hydrocarbon linkers to identify candidate bis-phosphinate ligands with the potential to bind preferentially to Ce-bastnäsite. Among the five most promising bis-phosphinate ligands suggested by theoretical studies, three ligands were synthesized and their adsorption characteristics to bastnäsite (100) interfaces were characterized using vibrational sum-frequency (vSFG) spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, and isothermal titration calorimetry (ITC). The efficacy of the selective interfacial molecular binding was demonstrated by identifying a bis-phosphinate ligand capable of providing an overall higher surface coverage of alkyl groups relative to a monophosphinate ligand. The results highlight the interplay between adsorption binding strength and maximum surface coverage in determining ligand efficiency to render the mineral surface hydrophobic. DFT calculations further indicate that all tested ligands have higher affinity for Ce-bastnäsite than for calcite. Finally, this is consistent with the ITC data showing stronger adsorption enthalpy to bastnäsite than to calcite, making these ligands promising candidates for selective flotation of Ce-bastnäsite.

58 GEOSCIENCES↗
DOE OSTI2025

Enhancing the Optically Detected Magnetic Resonance Signal of Organic Molecular Qubits

In quantum information science and sensing, electron spins are often purified into a specific polarization through an optical-spin interface, a process known as optically detected magnetic resonance (ODMR). Diamond-NV centers and transition metals are both excellent platforms for these so-called color centers, while metal-free molecular analogues are also gaining popularity for their extended polarization lifetimes, milder environmental impacts, and reduced costs. In our earlier attempt at designing such organic high-spin π-diradicals, we proposed to spin-polarize by shelving triplet M S = ±1 populations as singlets. This was recently verified by experiments albeit with low ODMR contrasts of <1% at temperatures above 5 K. In this work, we propose to improve the ODMR signal by moving singlet populations back into the triplet M S = 0 sublevel, designing a true carbon-based molecular analogue to the NV center. Our proposal is based upon transition-orbital and group-theoretical analyses of beyond-nearest-neighbor spin–orbit couplings, which are further confirmed by ab initio calculations of a realistic trityl-based radical dimer. Microkinetic analyses point toward high ODMR contrasts of around 30% under experimentally feasible conditions, a stark improvement from previous works. Finally, in our quest toward ground-state optically addressable molecular spin qubits, we exemplify how our symmetry-based design avoids Zeeman-induced singlet–triplet mixings, setting the scene for realizing electron spin qubit gates.

Group theory↗
DOE OSTI2026

Nanoconfined Grain Boundaries Increase the Conductivity of Polycrystalline Molecular Crystals

Soft-solid molecular crystals consist of crystalline grains and fluid grain boundaries (GBs) that enhance the grain binding and transport of Li + ions between the grains. The total ionic conductivity consists of ion migration in both the grains and GBs. To unravel these contributions in adiponitrile (Adpn):LiPF 6 molecular crystals, the GB volume fraction was varied by changing the size of the crystals and the Adpn:LiPF 6 molar ratio. Molecular dynamics (MD) simulations indicate that ion motion was subdiffusive in the grains and “well-diffusive” in the GBs, with GBs characterized as disordered nanoconfined regions of higher charge carrier concentration (∼1 M) than in saturated Adpn:LiPF 6 solutions (0.04 M), and Li + ions predominantly solvated by cyano groups with few contact ion pairs. The diffusivity in the GBs is at least an order of magnitude higher than that in the crystalline grains. The emergent picture is the grains as a reservoir of ions that migrate to faster-conducting GBs.

Crystals↗
DOE OSTI2023

Nanoscale Periodic Trapping Sites for Interlayer Excitons Built by Deformable Molecular Crystal on 2D Crystal

The nanoscale moiré pattern formed at 2D transition-metal dichalcogenide crystal (TMDC) heterostructures provides periodic trapping sites for excitons, which is essential for realizing various exotic phases such as artificial exciton lattices, Bose–Einstein condensates, and exciton insulators. At organic molecule/TMDC heterostructures, similar periodic potentials can be formed via other degrees of freedom. Here, we utilize the structure deformability of a 2D molecular crystal as a degree of freedom to create a periodic nanoscale potential that can trap interlayer excitons (IXs). Specifically, two semiconducting molecules, PTCDI and PTCDA, which possess similar band gaps and ionization potentials but form different lattice structures on MoS 2 , are investigated. The PTCDI lattice on MoS 2 is distorted geometrically, which lifts the degeneracy of the two molecules within the crystal’s unit cell. The degeneracy lifting results in a spatial variation of the molecular orbital energy, with an amplitude and periodicity of ~0.2 eV and ~2 nm, respectively. On the other hand, no such energy variation is observed in PTCDA/MoS 2 , where the PTCDA lattice is much less distorted. Furthermore, the periodic variation in molecular orbital energies provides effective trapping sites for IXs. For IXs formed at PTCDI/MoS 2 , rapid spatial localization of the electron in the organic layer toward the interface is observed, which demonstrates the effectiveness of these interfacial IX traps.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Leveraging Natural Language Processing and Generative Models in Molecular Chemistry: Property Prediction and Novel Compound Generation

The accurate prediction of molecular properties is important for the rational design and the advancement of green chemistry and sustainable materials research. However, the predictive power of traditional computational chemistry methods is limited due to computational restrictions. Here, in this study, we examine an alternative approach to the accurate prediction of properties of organic compounds: natural language processing (NLP)-based molecular embedding. Using viscosity, partition coefficient (log P), and enthalpy of vaporization as test properties through a survey of comprehensive datasets comprising 5695 data points for viscosity, 25 870 data points for log P, and 2296 data points for enthalpy of vaporization. These are important properties for the design of greener, safer, and sustainable chemical processes. Models were trained using NLP methods such as Mol2vec and fine-tuned ChemBERTa, and results were compared with traditional input featurization techniques such as Morgan fingerprints and quantum chemistry derived sigma profiles and DFT features. Among the various machine learning models, Mol2vec demonstrated superior predictive capabilities, achieving the highest correlation coefficient (R 2 = 0.945) and lowest RMSE (0.106 mPa s) for viscosity, as well as high accuracy for log P and enthalpy of vaporization predictions. These findings establish the Mol2vec featurization technique, graph-convolutional neural networks (GCNN), and fine-tuned ChemBERTa model as powerful tools for predictive modeling of organic compounds properties, offering a significant improvement over previously used featurization techniques and opening up strategies for very-high-throughput computational screening. Finally, we integrated ML models with hybrid language-model-based generative adversarial networks (LM-GAN) to generate novel molecular sequences with desirable properties for different research applications. The ability to computationally design solvents with lower viscosity, lower log P, and lower enthalpy of vaporization offers a data-driven route to accelerating the discovery of sustainable alternatives to traditionally toxic solvents.

ChemBERTa↗
DOE OSTI2021

Buffered Coordination Modulation as a Means of Controlling Crystal Morphology and Molecular Diffusion in an Anisotropic Metal-Organic Framework

We know significant advances have been made in the synthesis of chemically selective environments within metal-organic frameworks, yet materials development and industrial implementation have been hindered by the inability to predictively control crystallite size and shape. One common strategy to control crystal growth is the inclusion of coordination modulators, which are molecular species designed to compete with the linker for metal coordination during synthesis. However, these modulators can simultaneously alter the pH of the reaction solution, an effect that can also significantly influence crystal morphology. Herein, noncoordinating buffers are used to independently control reaction pH during metal-organic framework synthesis, enabling direct interrogation of the role of the coordinating species on crystal growth. We demonstrate the efficacy of this strategy in the synthesis of low-dispersity single-crystals of the framework Co 2 (dobdc) (dobdc 4- = 2,5-dioxido-1,4-benzenedicarboxylate) in a pH 7-buffered solution using cobalt(II) acetate as the metal source. Density functional theory calculations reveal that acetate competitively binds to Co during crystallization, and by using a series of cobalt(II) salts with carboxylate anions of varying coordination strength, it is possible to control crystal growth along the c -direction. Finally, we use zero length column chromatography to show that crystal morphology has a direct impact on guest diffusional path length for the industrially important hydrocarbon m -xylene. Together, these results provide molecular-level insight into the use of modulators in governing crystallite morphology and a powerful strategy for the control of molecular diffusion rates within metal-organic frameworks.

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

Time-Evolving Chirality Loss in Molecular Photodissociation Monitored by X-ray Circular Dichroism Spectroscopy

In this work, the ultrafast photoinduced chirality loss of 2-iodobutane is studied theoretically by time- and frequency-resolved X-ray circular dichroism (TRXCD) spectroscopy. Following an optical excitation, the iodine atom dissociates from the chiral center, which we capture by quantum non-adiabatic molecular dynamics simulations. At variable time delays after the pump, the resonant X-ray pulse selectively probes the iodine and carbon atom involved in the chiral dissociation through a selected core-to-valence transition. The TRXCD signal at the iodine L 1 edge accurately captures the timing of C–I photodissociation and thereby chirality loss, c.a 70 fs. The strong electric dipole–electric quadrupole (ED–EQ) response makes this signal particularly sensitive to vibronic coherence at the high X-ray regime. At the carbon K-edges, the signals monitor the molecular chirality of the 2-butyl radical photoproduct and the spin state of the iodine atom. The ED–EQ response is masked under the strong electric dipole-magnetic dipole response, making this signal intuitive for the electronic population. The evolution of the core electronic states and its chiral sensitivity is discussed. Overall, the element-specific TRXCD signal provides a detailed picture of molecular dynamics and offers a unique sensitive window into the time-dependent chirality of molecules.

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

Illuminating Ligand Field Contributions to Molecular Qubit Spin Relaxation via T 1 Anisotropy

Electron spin relaxation in paramagnetic transition metal complexes constitutes a key limitation on the growth of molecular quantum information science. However, there exist very few experimental observables for probing spin relaxation mechanisms, leading to a proliferation of inconsistent theoretical models. Here we demonstrate that spin relaxation anisotropy in pulsed electron paramagnetic resonance is a powerful spectroscopic probe for molecular spin dynamics across a library of highly coherent Cu(II) and V(IV) complexes. Here, neither the static spin Hamiltonian anisotropy nor contemporary computational models of spin relaxation are able to account for the experimental T 1 anisotropy. Through analysis of the spin-orbit coupled wavefunctions, we derive an analytical theory for the T 1 anisotropy that accurately reproduces the average experimental anisotropy of 2.5. Furthermore, compound-by-compound deviations from the average anisotropy provide a promising approach for observing specific ligand field and vibronic excited state coupling effects on spin relaxation. Finally, we present a simple density functional theory workflow for computationally predicting T 1 anisotropy. Analysis of spin relaxation anisotropy leads to deeper fundamental understanding of spin-phonon coupling and relaxation mechanisms, promising to complement temperature-dependent relaxation rates as a key metric for understanding molecular spin qubits.

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

Direct Transformation of SiH 4 to a Molecular L(H) 2 Co=Si=Co(H) 2 L Silicide Complex

The synthesis of bimetallic molecular silicide complexes is reported, based on the use of multiple Si–H bond activations in SiH 4 at the metal centers of 14-electron LCo I fragments (L = Tp", HB(3,5-diisopropylpyrazolyl) 3 – ; [BP 2 tBu Pz], PhB(CH 2 P t Bu 2 ) 2 (pyrazolyl)). Upon exposure of (Tp"Co) 2 (μ-N 2 ) (1) to SiH 4 , a mixture of (Tp"Co) 2 (μ-H) (2) and (Tp"Co) 2 (μ-H) 2 (3) was formed and no evidence for Si–H oxidative addition products was observed. In contrast, [BP 2 tBu Pz]-supported Co complexes led to Si–H oxidative additions with the generation of silylene and silicide complexes as products. Notably, the reaction of ([BP 2 tBu Pz]Co) 2 (μ-N 2 ) (5) with SiH 4 gave the dicobalt silicide complex [BP 2 tBu Pz](H) 2 Co=Si=Co(H) 2 [BP 2 tBu Pz] (8) in high yield, representing the first direct route to a symmetrical bimetallic silicide. Here, the effect of the [BP 2 tBu Pz] ligand on Co–Si bonding in 7 and 8 was explored by analysis of solid-state molecular structures and density functional theory (DFT) investigations. Upon exposure to CO or DMAP (DMAP = 4-dimethylaminopyridine), 8 converted to the corresponding [BP 2 tBu Pz]Co(L) x adducts (L = CO, x = 2; L = DMAP, x = 1) with concomitant loss of SiH 4 , despite the lack of significant Si–H interactions in the starting complex. On heating to 60 °C, 8 underwent reaction with MeCl to produce small quantities of Me x SiH 4–x (x = 1–3), demonstrating functionalization of the μ-silicon atom in a molecular silicide to form organosilanes.

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

Infrared Spectroscopic Observation of Oxo- and Superoxo-Intermediates in the Water Oxidation Cycle of a Molecular Ir Catalyst

Molecular Ir catalysts have emerged as an important class of model catalysts for understanding structure–activity relationships in water oxidation, a reaction that is central to renewable fuel synthesis. Prior efforts have mostly focused on controlling and elucidating the emergence of active species from prepared precursors. However, the development of efficient and stable molecular Ir catalysts also necessitates probing of reaction intermediates. To date, relatively little is known about the key intermediates in the cycles of the molecular Ir catalysts. Herein, we probed the catalytic cycle of a homogeneous Ir catalyst (“blue dimer”) at a Au electrode/aqueous electrolyte interface by combining surface-enhanced infrared absorption spectroscopy (SEIRAS) with phase-sensitive detection (PSD). Cyclic voltammograms (CVs) from 1.4 to 1.7 VRHE (RHE = reversible hydrogen electrode) give rise to a band at ~818 cm –1 , whereas CVs from 1.4 to ≥1.85 VRHE generate an additional band at ~1146 cm –1 . Isotope labeling experiments indicate that the bands at ~818 and ~1146 cm –1 are attributable to oxo (Ir V =O) and superoxo (Ir IV –OO • ) moieties, respectively. Furthermore, this study establishes PSD-SEIRAS as a sensitive tool for probing water oxidation cycles at electrode/electrolyte interfaces and demonstrates that the relative abundance of two key intermediates can be tuned by the thermodynamic driving force of the reaction.

25 ENERGY STORAGE↗
DOE OSTI2025

Photodriven Ammonia Synthesis from N 2 and H 2 : Recycling of a Molecular Molybdenum Nitride

Here, the synthesis of ammonia from its elements, N 2 and H 2 , is the most atom-economical and thermodynamically preferred route but presents a high kinetic barrier and thus is rare using molecular compounds. Irradiation of a molecular molybdenum nitride prepared from N 2 cleavage with visible light in the presence of an iridium photocatalyst and 1–4 atm of H 2 produced high yields of ammonia along with the formation of a cationic, formally molybdenum(VI) pentahydride as the major molybdenum-containing product. Continued irradiation of the molybdenum hydride under an N 2 atmosphere resulted in regeneration of the molybdenum nitride that was recycled and used for additional hydrogenation to generate more ammonia, demonstrating superstoichiometric batch ammonia synthesis using only N 2 and H 2 with molecular compounds under ambient conditions.

Hydrogenation↗
DOE OSTI2025

Amplifying Magnetic Field Effects on Upconversion Emission via Molecular Qubit-Driven Triplet–Triplet Annihilation

Triplet-triplet annihilation (TTA) enables photon upconversion by combining two lower-energy triplet excitons to produce a higher-energy singlet exciton. This mechanism enhances light-harvesting efficiency for solar energy conversion and enables the use of lower-energy photons in bioimaging and photoredox catalysis applications. The magnetic modulation of such high-energy excitons presents an exciting opportunity to develop molecular quantum information technologies. While the spin dynamics of triplet exciton pairs are sensitive to external magnetic fields, the magnetic field effects (MFEs) associated with these pairs are generally limited by spin statistics to at most 10% at low fields (<1 Tesla), making them challenging to apply in technological advancements. In contrast, MFEs on spin-correlated radical pairs (SCRPs) can be significantly greater, surpassing those on triplet pairs. By using SCRPs-based molecular qubits as triplet sensitizers in the sensitized TTA scheme, we can magnetically modulate TTA and consequently, the delayed fluorescence of annihilators. In our current system, we have achieved more than 70% magnetic modulation of delayed fluorescence, effectively harnessing and even amplifying magnetic modulation within SCRPs to influence high-energy excitons. In conclusion, this work opens new opportunities for advancing spin-controlled chemical reactions and molecular quantum information technologies.

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

Mechanistic Insights into Molecular Copper Hydride Catalysis: the Kinetic Stability of CuH Monomers toward Aggregation is a Critical Parameter for Catalyst Performance

The activity of molecular copper hydride (CuH) complexes towards the selective insertion of unsaturated hydrocarbons under mild conditions has contributed significantly to versatile methodologies for upgrading these feedstocks. However, these catalysts are particularly susceptible to deleterious aggregation, leading to the depletion of active CuH species. Little is known about the mechanisms of CuH aggregation, how it influences overall catalyst performance, and how it can be controlled. We address these challenges with mechanistic studies on a model reaction of unactivated alkene hydroboration catalyzed by (IPr*CPh 3 )CuH (LCuH). Here, we report a comprehensive mechanistic investigation of this system, identifying an aggregation pathway that continuously depletes catalytically active LCuH to form inactive CuH clusters during turnover. Deactivation of LCuH is controlled primarily by the competition between the kinetics of the initial LCuH dimerization step and that of alkene insertion. We therefore propose that a more comprehensive understanding of CuH catalyst performance must account for the kinetics of the initial LCuH dimerization step, revising a previously explored thermodynamic understanding of CuH aggregation, where the concentration of active species is controlled by equilibria established between CuH dimers and monomers. With a series of (NHC)CuH congeners (NHC = N-heterocyclic carbene), we demonstrate that ostensibly minor structural modifications to the ligand peripheries can drastically affect the LCuH dimerization kinetics, while maintaining reactivity towards on–cycle alkene insertion. We employed a computational approach based on molecular dynamics simulations to provide an in-depth understanding of how specific structural ligand modifications can substantially increase the kinetic stability of monomeric CuH catalysts. Our combined experimental and computational studies suggest strategies for rational ligand design that can be broadly applied to molecular catalyst systems that are susceptible to deactivation via aggregation pathways.

Ryan, David E. [Pacific Northwest National Laborat↗
DOE OSTI2025

Tetracene Functionalized Si(111) Achieves Enhanced Solar-to-Chemical Energy Conversion via Molecular Acceptor States

The properties of semiconductor|liquid interfaces play a critical role in determining the efficiency of solar-to-hydrogen (STH) conversion. Here, we investigate how molecular functionalization of Si(111) and Si(111)|TiO 2 surfaces impacts photoelectrochemical (PEC) hydrogen production efficiency. We find that functionalization of ∼3% of the atop sites of Si(111) with either 9-anthracene (Anth) or 5-tetracene (Tet), with the remaining sites passivated by methyl groups, provides substrates with high electronic quality and low surface oxide densities, as determined by X-ray photoelectron spectroscopy (XPS) measurements. Surface photovoltage (SPV) spectroscopy shows that surfaces modified with Anth or Tet exhibit an increased photovoltage, with Tet-functionalized surfaces yielding an additional 192 meV relative to methyl-terminated Si(111), indicating improved charge separation for Si-Tet. Further improvement in onset potential was achieved by replacing a nitrogen-containing TiO 2 atomic layer deposition (ALD) precursor (TDMAT) with a precursor lacking nitrogen (TTIP), which eliminates the parasitic defect band in the TiO 2 overlayer (p-Si(111)-Tet|TTIP-TiO 2 |Pt: V OC = +0.283 ± 0.041 V vs RHE). Density functional theory (DFT) analysis demonstrates that compared with Anth-modified Si(111), the Tet-modified surface exhibits more hybridized Si(111)-Tet states closer to the silicon band edges. Mercury contact current–voltage (I–V, dark) measurements quantified the relative interfacial density of states of Si-Tet, Si-Anth and Si-Me surfaces─revealing that the interfacial state density was highest for Si-Tet. This suggests that such hybridized interfaces serve to capture better photoexcited charge, which enables facile electron transfer to molecular acceptors in solution. Altogether, the data indicate that beneficial hybrid molecular LUMO surface states interacting with the Si conduction band edge results in improved hydrogen evolution (HER) performance for p-Si devices.

Group theory↗
DOE OSTI2026

Leveraging 13C-Labeling to Assign Molecular Formulas to Unknown Yeast Metabolites

Mass spectrometry analyses have identified tens of thousands of unknown small molecule-associated peaks in different biological specimens. Notably, even the simplest and best studied organisms like Escherichia coli and Saccharomyces cerevisiae yield thousands of unknown peaks. A key question is how many of these reflect actual novel endogenous metabolites. To explore this, Mahieu and Patti used complete 13 C -labeling in E. coli to credential peaks as biological. This reduced the number of unknowns by more than 90%. Here, we carry out similar uniform 13 C-labeling in the Baker’s yeast S. cerevisiae and two less-studied bioenergy-relevant yeasts Rhodotorula toruloides (lipid producer) and Issatchenkia orientalis (organic acid producer). Identification of unknown metabolite peaks and their molecular formulas is facilitated through software tailored for 13 C labeling data and resulting knowledge of carbon atom count. A classification model evaluates the plausibility of each candidate formula, with peaks lacking plausible candidate formulas unlikely to reflect metabolite molecular ions. This approach prioritizes about one hundred candidate abundant unknown metabolites with logical molecular formulas. Most of these are species-specific rather than conserved across yeasts, and more are found in the nonmodel yeasts than S. cerevisiae. Thus, 13 C-labeling data on unknown metabolites highlights the potential for discovering new metabolites and pathways in nonmodel yeasts.

Carbon↗
DOE OSTI2024

Photolytic Degradation of Water‐Soluble Organic Carbon in Snowmelts: Changes in Molecular Characteristics, Brown Carbon Chromophores, and Radiative Effects

Abstract Water‐soluble organic carbon (WSOC) deposited in ambient snowpack play key roles in regional carbon cycle and surface energy budget, but the impacts of photo‐induced processes on its optical and chemical properties are poorly understood yet. In this study, melted samples of the seasonal snow collected from northern Xinjiang, northwestern China, were exposed to ultraviolet (UV) radiation to investigate the photolytic transformations of WSOC. Molecular characteristics and chemical composition of WSOC and its brown carbon (BrC) constituents were investigated using high‐performance liquid chromatography interfaced with a photodiode array detector and a high‐resolution mass spectrometer. Upon illumination, formation of nitrogen‐ and sulfur‐containing species with high molecular weight was observed in snow samples influenced by soil‐ and plant‐derived organics. In contrast, the representative sample collected from remote region showed the lowest molecular diversity and photolytic reactivity among all samples, in which no identified BrC chromophores decomposed upon illumination. Approximately 65% of chromophores in urban samples endured UV irradiation. However, most of BrC composed of phenolic/lignin‐derived compounds and flavonoids disappeared in the illuminated samples containing WSOC from soil‐ and plant‐related sources. Effects of the photochemical degradation of WSOC on the potential modulation of snow albedo were estimated. Apparent half‐lives of WSOC estimated as albedo reduction in 300–400 nm indicated 0.1–0.4 atmospheric equivalent days, which are shorter than typical photolysis half‐lives of ambient biomass smoke aerosol. This study provides new insights into the roles of WSOC in snow photochemistry and snow surface energy balance.

Meteorology & Atmospheric Sciences↗
DOE OSTI2021

Molecular bridge-mediated ultralow-power gas sensing

Abstract We report the electrical detection of captured gases through measurement of the quantum tunneling characteristics of gas-mediated molecular junctions formed across nanogaps. The gas-sensing nanogap device consists of a pair of vertically stacked gold electrodes separated by an insulating 6 nm spacer (~1.5 nm of sputtered α-Si and ~4.5 nm ALD SiO 2 ), which is notched ~10 nm into the stack between the gold electrodes. The exposed gold surface is functionalized with a self-assembled monolayer (SAM) of conjugated thiol linker molecules. When the device is exposed to a target gas (1,5-diaminopentane), the SAM layer electrostatically captures the target gas molecules, forming a molecular bridge across the nanogap. The gas capture lowers the barrier potential for electron tunneling across the notched edge region, from ~5 eV to ~0.9 eV and establishes additional conducting paths for charge transport between the gold electrodes, leading to a substantial decrease in junction resistance. We demonstrated an output resistance change of >10 8 times upon exposure to 80 ppm diamine target gas as well as ultralow standby power consumption of <15 pW, confirming electron tunneling through molecular bridges for ultralow-power gas sensing.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Manipulating electron redistribution to achieve electronic pyroelectricity in molecular [FeCo] crystals

Pyroelectricity plays a crucial role in modern sensors and energy conversion devices. However, obtaining materials with large and nearly constant pyroelectric coefficients over a wide temperature range for practical uses remains a formidable challenge. Attempting to discover a solution to this obstacle, we combined molecular design of labile electronic structure with the crystal engineering of the molecular orientation in lattice. This combination results in electronic pyroelectricity of purely molecular origin. Here, we report a polar crystal of an [FeCo] dinuclear complex exhibiting a peculiar pyroelectric behavior (a substantial sharp pyroelectric current peak and an unusual continuous pyroelectric current at higher temperatures) which is caused by a combination of Fe spin crossover (SCO) and electron transfer between the high-spin Fe ion and redox-active ligand, namely valence tautomerism (VT). As a result, temperature dependence of the pyroelectric behavior reported here is opposite from conventional ferroelectrics and originates from a transition between three distinct electronic structures. The obtained pyroelectric coefficient is comparable to that of polyvinylidene difluoride at room temperature.

36 MATERIALS SCIENCE↗