Cryogenic Photodetachment Spectroscopy and High-Resolution Resonant Photoelectron Imaging of Cold para -Ethylphenolate Anions
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
SEARCH · Engineering Papers
Results for “Vibrational Spectroscopy”
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Vibronic coupling in light-harvesting complex II revisited
A growing body of work has pointed to vibronic mixing as a crucial design principle for efficient energy and charge transfer in natural and artificial systems.= Notable among these studies was the recent observation of vibronically promoted ultrafast energy flow in the major antenna complex of green plants and algae light-harvesting complex II (LHCII)—the most abundant membrane protein on the Earth—via the emerging experimental technique two-dimensional electronic-vibrational (2DEV) spectroscopy. This spectroscopy, which correlates electronic and nuclear degrees-of-freedom, shows promise for providing mechanistic insight into vibronic coupling; however, explicit theoretical input is necessary to extract such a detail. In a separate paper, we have developed a heterodimer model that describes various forms of vibronic coupling—which were speculated to be present in LHCII—resulting from diagonal electron–phonon coupling giving Franck–Condon (FC) activity and the nuclear dependence of the electronic transition dipole moment giving Herzberg–Teller (HT) activity. Here, we draw connections between this theoretical work and recent experimental studies in order to demonstrate how HT activity is leveraged in the function of LHCII.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Semi-empirical quantum optics for mid-infrared molecular nanophotonics
Nanoscale infrared (IR) resonators with sub-diffraction limited mode volumes and open geometries have emerged as new platforms for implementing cavity quantum electrodynamics at room temperature. The use of IR nanoantennas and tip nanoprobes to study strong light–matter coupling of molecular vibrations with the vacuum field can be exploited for IR quantum control with nanometer spatial and femtosecond temporal resolution. In order to advance the development of molecule-based quantum nanophotonics in the mid-IR, we propose a generally applicable semi-empirical methodology based on quantum optics to describe light–matter interaction in systems driven by mid-IR femtosecond laser pulses. The theory is shown to reproduce recent experiments on the acceleration of the vibrational relaxation rate in infrared nanostructures. It also provides physical insights on the implementation of coherent phase rotations of the near-field using broadband nanotips. We then apply the quantum framework to develop general tip-design rules for the experimental manipulation of vibrational strong coupling and Fano interference effects in open infrared resonators. We finally propose the possibility of transferring the natural anharmonicity of molecular vibrational levels to the resonator near-field in the weak coupling regime to implement intensity-dependent phase shifts of the coupled system response with strong pulses and develop a vibrational chirping model to understand the effect. The semi-empirical quantum theory is equivalent to first-principles techniques based on Maxwell’s equations, but its lower computational cost suggests its use as a rapid design tool for the development of strongly coupled infrared nanophotonic hardware for applications ranging from quantum control of materials to quantum information processing.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Microhydration of the metastable N -Protomer of 4-Aminobenzoic acid by condensation at 80 K: H/D exchange without conversion to the more stable O- protomer
4-Aminobenzoic acid (4ABA) is a model scaffold for studying solvent-mediated proton transfer. Although protonation at the carboxylic group (O-protomer) is energetically favored in the gas phase, the N-protomer, where the proton remains on the amino group, can be kinetically trapped by electrospray ionization of 4ABA in an aprotic solvent such as acetonitrile. Here we report the formation of the hydrated deuterium isotopologues of the N-protomers, RND 3 + ·(H 2 O) n=1-3 , (R=C 6 H 4 COOD), which are generated by condensing water molecules onto the bare N-protomers in a liquid nitrogen cooled, radiofrequency octopole ion trap at 80 K. The product clusters are then transferred to a 20 K cryogenic ion trap where they are tagged with weakly bound D 2 molecules. The structures of these clusters are determined by analysis of their vibrational patterns obtained by resonant IR photodissociation. The resulting patterns confirm that the metastable N-protomer configuration remains intact even when warmed by sequential condensation of water molecules. Attachment of H 2 O molecules onto the RND 3 + head group also affords the opportunity to explore the possibility of H/D exchange between the acid scaffold and the proximal water network. The spectroscopic results establish that although the RND 3 + ·(H 2 O) n=1,2 clusters are formed without H/D exchange, the n = 3 cluster exhibits about 10% H/D exchange as evidenced by the appearance of the telltale HOD bands. Furthermore, the site of exchange on the acid is determined to be the acidic OH by the emergence of the OH stretching fundamental in the -COOH motif.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
From antenna to reaction center: Pathways of ultrafast energy and charge transfer in photosystem II
The photosystem II core complex (PSII-CC) is the smallest subunit of the oxygenic photosynthetic apparatus that contains core antennas and a reaction center, which together allow for rapid energy transfer and charge separation, ultimately leading to efficient solar energy conversion. However, there is a lack of consensus on the interplay between the energy transfer and charge separation dynamics of the core complex. Here, we report the application of two-dimensional electronic-vibrational (2DEV) spectroscopy to the spinach PSII-CC at 77 K. The simultaneous temporal and spectral resolution afforded by 2DEV spectroscopy facilitates the separation and direct assignment of coexisting dynamical processes. Our results show that the dominant dynamics of the PSII-CC are distinct in different excitation energy regions. By separating the excitation regions, we are able to distinguish the intraprotein dynamics and interprotein energy transfer. Additionally, with the improved resolution, we are able to identify the key pigments involved in the pathways, allowing for a direct connection between dynamical and structural information. Specifically, we show that C505 in CP43 and the peripheral chlorophyll Chlz D1 in the reaction center are most likely responsible for energy transfer from CP43 to the reaction center.
59 BASIC BIOLOGICAL SCIENCES↗
Understanding the electron-water interaction at the molecular level: Integrating theory and experiment in the cluster regime
In this final technical report, we summarize our major accomplishments resulting from a combined experimental-theoretical approach that exploits the unique properties of molecular clusters to elucidate how local interactions at the molecular level drive the macroscopic behavior of materials and chemical transformations in liquids. The specific targets for our efforts have need to elucidate how charged entities are accommodated by hydrogen-bonding networks and to establish how the behavior of room temperature ionic liquids can be tailored for specific chemical applications. Because of their central importance in aqueous electrolyte chemistry, we have placed particular emphasis understanding the accommodation of excess electrons and protons by water. These surprisingly complex fundamental electrical charges play a fundamental role in a wide range of chemical and biological processes, and yet even a qualitative picture of their speciation in water and at the air-water interface has proven elusive. The main experimental diagnostic in our approach is to measure and analyze vibrational spectra of temperature and composition controlled molecular aggregates that isolate and amplify the spectral markers for local interactions that are often obscured in measurement on bulk or interfacial water. Our combined experimental-theoretical program has led to a greatly enhanced understanding of the nature of excess electrons and protons in water and in the process developed new and powerful methods of chemical analysis that are currently in use across the chemical sciences.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Understanding the role of negative charge in the scaffold of an artificial enzyme for CO 2 hydrogenation on catalysis
Here, we have approached the construction of an artificial enzyme by employing a robust protein scaffold, lactococcal multidrug resistance regulator, LmrR, providing a structured secondary and outer coordination spheres around a molecular rhodium complex, [Rh I (P Et2 N gly P Et2 ) 2 ] - . Previously, we demonstrated a 2–3 fold increase in activity for one Rh-LmrR construct by introducing positive charge in the secondary coordination sphere. In this study, a series of variants was made through site-directed mutagenesis where the negative charge is located in the secondary sphere or outer coordination sphere, with additional variants made with increasingly negative charge in the outer coordination sphere while keeping a positive charge in the secondary sphere. Placing a negative charge in the secondary or outer coordination sphere demonstrates decreased activity by a factor of two compared to the wild-type Rh-LmrR. Interestingly, addition of positive charge in the secondary sphere, with the negatively charged outer coordination sphere restores activity. Vibrational and NMR spectroscopy suggest minimal changes to the electronic density at the rhodium center, regardless of inclusion of a negative or positive charge in the secondary sphere, suggesting another mechanism is impacting catalytic activity, explored in the discussion.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
New Perspectives on Vibrational Energy Transfer in Energetic Materials: Insights from Pressure-Tuned Ultrafast Spectroscopy
Understanding the manner in which vibrational energy flows between molecular and lattice vibrations is of great interest in physical chemistry due to its central role in reactivity and energy dissipation in molecular materials. Here, in this feature article, we highlight our recent efforts employing ultrafast broadband infrared spectroscopy toward understanding the interplay between molecular and lattice vibrations in energetic materials, motivated by the open questions surrounding the role of vibrational energy transfer (VET) in reaction initiation in these materials. Our work addresses the ongoing debate on the participation of doorway modes in VET. We further present new results from high-pressure ultrafast experiments on RDX, a hydrogen-bonded material, and BNFF, a hydrogen-free material, to explore how intermolecular interaction strength governs VET pathways and time scales. Collectively, our findings reveal that vibrational dynamics in these systems occurs across three distinct time regimes, with VET being incomplete out to hundreds of picoseconds, suggesting the importance of considering nonstatistical reactions in the modeling of these materials. These time scales vary as intermolecular interaction strength is indirectly modified by application of static pressure, indicating dramatic changes to the vibrational structure of these materials under shock-relevant conditions. Our results thus shed light on how intermolecular interactions shape vibrational energy redistribution in molecular materials, and highlight the need for further theoretical and experimental investigation.
Carlson, Daniel Ryan [Sandia National Laboratories↗
Raman Spectroscopy Characterization of Nuclear Materials and Soot from High Explosives
Vibrational and luminescence spectroscopy were used in the investigation of U and Pu-bearing compounds and soot from high explosives testing. Key spectroscopic signatures of UF4 and its hydrates, PuO 2 , and soot from different explosives will be presented. The United States Government retains and the publisher, by accepting this article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for United States Government purposes.
Villa-Aleman, Eliel↗
Mixed ortho- H 2 and para- H 2 clusters studied by vibrational coherent anti-Stokes Raman spectroscopy
The search for macroscopic quantum effects, including superfluidity, in molecular hydrogen is mostly focused on its parahydrogen (p-H 2 ) nuclear spin modification because of weaker intermolecular interaction compared to orthohydrogen (o-H 2 ), both modifications being bosonic. In this work, mixed clusters of o-H 2 and p-H 2 containing similar to 10(4) molecules are prepared by supersonic expansion with helium and studied by vibrational coherent anti-Stokes Raman scattering (CARS) spectroscopy. At similar experimental conditions the neat p-H 2 clusters avoid freezing and remain fluid at 1-2 K, which is predicted to be the realm of their superfluid behavior [Phys. Rev. Lett. 101, 205301 (2008)]. Dependence of the vibrational frequencies and intensities of the main CARS peaks due to o-H 2 and p-H 2 versus the ratio of the o-H 2 and p-H 2 concentrations in the expanding gas suggests that o-H 2 and p-H 2 molecules are uniformly mixed in the interior of the clusters. A weak spectral feature at 4157 cm -1 that appears independent of the concentration ratio is assigned to the outer shell of the clusters enriched with p-H 2 molecules. Although the phase of the mixed clusters could not be unambiguously identified, the shift of the vibrational frequencies with respect to the bulk solid is consistent with the liquid state of the clusters.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Surface Functionalization of Black Phosphorus with Nitrenes: Identification of P=N Bonds Using Isotopic Labeling
Abstract: Surface functionalization of two-dimensional crystals is a key path to tuning their intrinsic physical and chemical properties. However, synthetic protocols and experimental strategies to directly probe chemical bonding in modified surfaces are scarce. Introduced here is a mild, surface-specific protocol for the surface functionalization of few-layer black phosphorus nanosheets using a family of photolytically generated nitrenes (RN) from the corresponding azides. By embedding spectroscopic tags in the organic backbone, a multitude of characterization techniques are employed to investigate in detail the chemical structure of the modified nanosheets, including vibrational (infrared, Raman), Xray (emission, photoelectron), CPMAS NMR, and UV-vis spectroscopy. To directly probe the functional groups introduced on the surface, R fragments were selected such that in conjunction with vibrational spectroscopy, 15N-labeling experiments, and DFT methods, diagnostic P=N vibrational modes indicative of iminophosphorane units on the nanosheet surface could be conclusively identified.
Walz, Kendall↗
Understanding Self-Assembly and the Stabilization of Liquid/Liquid Interfaces: The Importance of Ligand Tail Branching and Oil-Phase Solvation
Organophosphorus-based ligands represent a versatile set of solvent extraction reagents whose chemical makeup plays an important role in extraction mechanism. We hypothesize that the branching of the extractant hydrophobic tail and its oil-phase solvation affect the liquid/liquid interfacial structure. Understanding the structure mediated adsorption and interfacial ordering becomes key in designing ligands with enhanced selectivity and efficiency for targeted extractions. We employed vibrational sum frequency generation spectroscopy and interfacial tension measurements to extract thermodynamic adsorption energies, map interfacial ordering, and rationalize disparate behaviors of model di-(2-ethylhexyl) phosphoric acid and dioctyl phosphoric acid ligands at the hexadecane water interface. With increased surface loading, ligands with branched hydrophobic tails formed stable interfaces at much lower concentrations than those observed for ligands with linear alkyl tails. The lack of an oil phase and associated solvation results in markedly different interfacial properties, and thus measurements made at air/liquid surfaces cannot be assumed to correlate with the processes occurring at buried liquid/liquid interfaces. Here, we attribute these differences in the surface mediated self-assembly to key variations in hydrophobic interactions and tail solvation taking place in the oil phase demonstrating that interactions in both the polar and nonpolar phases are essential to understand self-assembly and function.
36 MATERIALS SCIENCE↗
Surface Functionalization of Black Phosphorus with Nitrenes: Identification of P=N Bonds by Using Isotopic Labeling
Abstract Surface functionalization of two‐dimensional crystals is a key path to tuning their intrinsic physical and chemical properties. However, synthetic protocols and experimental strategies to directly probe chemical bonding in modified surfaces are scarce. Introduced herein is a mild, surface‐specific protocol for the surface functionalization of few‐layer black phosphorus nanosheets using a family of photolytically generated nitrenes (RN) from the corresponding azides. By embedding spectroscopic tags in the organic backbone, a multitude of characterization techniques are employed to investigate in detail the chemical structure of the modified nanosheets, including vibrational, X‐ray photoelectron, solid state 31 P NMR, and UV‐vis spectroscopy. To directly probe the functional groups introduced on the surface, R fragments were selected such that in conjunction with vibrational spectroscopy, 15 N‐labeling experiments, and DFT methods, diagnostic P=N vibrational modes indicative of iminophosphorane units on the nanosheet surface could be conclusively identified.
Walz Mitra, Kendahl L.↗
Ultrafast spectroscopic studies of vibrational energy transfer in energetic materials
Shock-induced detonation is a key property of energetic materials (EM) that remains empirically understood. One proposed mechanism of shock-initiation in EM is “phonon up-pumping” to initiate chemical reactions, where excitation of lattice phonon modes rapidly transfers energy into intramolecular vibrations, ultimately resulting in the breaking of chemical bonds. We are developing novel ultrafast laser spectroscopy techniques to study vibrational energy transfer from phonon modes to intramolecular vibrations (phonon up-pumping), as well as competing energy transfer pathways from intramolecular vibrations to phonon modes (vibrational cooling). Through combinations of plasma- generated supercontinuum infrared, tunable near- and mid-infrared, and terahertz pulses in pump-probe spectroscopy, supplemented with ab inito simulations, we can explore the energy transfer processes on a sub-picosecond time scale to elucidate vibrational energy transfer pathways and lifetimes in EM. In this work, we highlight recent progress, including the spectral and temporal characteristics of the infrared and THz sources as well as preliminary results on select EM.
36 MATERIALS SCIENCE↗
Improving Rare-Earth Mineral Separation with Insights from Molecular Recognition: Functionalized Hydroxamic Acid Adsorption onto Bastnäsite and Calcite
Enhancing the separation of rare-earth elements (REEs) from gangue materials in mined ores requires an understanding of the fundamental interactions driving the adsorption of collector ligands onto mineral interfaces. In this work, we examine five functionalized hydroxamic acid ligands as potential collectors for the REE-containing bastnäsite mineral in froth flotation using density functional theory calculations and a suite of surface-sensitive analytical spectroscopies. These include vibrational sum frequency generation, attenuated total reflectance Fourier transform infrared, Raman, and X-ray photoelectron spectroscopies. Differences in the chemical makeup of these ligands on well-defined bastnäsite and calcite surfaces allow for a systematic relationship connecting the structure to adsorption activity to be framed in the context of interfacial molecular recognition. Here we show how the intramolecular hydrogen bonding of adsorbed ligands requires the inclusion of explicit water solvent molecules to correctly map energetic and structural trends measured by experiments. We anticipate that the results and insights from this work will motivate and inform the design of improved flotation collectors for REE ores.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Optical spectroscopy of molten fluorides: Methods, electronic and vibrational data, structural interpretation, and relevance to radiative heat transfer
In this study, to help address the need for predicting radiative heat transfer (RHT) behavior of molten salts, we conducted a comprehensive review of methods and data from optical spectroscopic measurements on molten fluoride salts. Transmittance, reflectance, and trans-reflectance experimental methods are discussed, along with the corresponding data reduction methodology and the limitations of each technique. Optical spectroscopy is a convenient indirect probe for changes in structural parameters with temperature and composition. Electronic and vibrational absorption data for transition-metal, lanthanide, and actinide solutes and vibrational absorption data for alkali and alkaline earth fluoride solvents are compiled, and the corresponding structural interpretation is discussed and compared with other experimental and theoretical work. We find that solvent and solute vibrational absorption can be significant in the mid-infrared, resulting in near-infrared edges of significance to RHT. Extrapolation and averaging of existing edge data leads to estimated gray absorption coefficient values at 700 °C of 546 m —1 for FLiBe and 276 m —1 for FLiNaK, both within the range of 1 – 6000 m —1 identified to be of engineering relevance for radiative heat transfer analysis.
36 MATERIALS SCIENCE↗
Sputter-Coated TiO 2 Films as Passivation and Hole Transfer Layers for Improved Energy Conversion with Solar Fuel WO 3 /CuWO 4 Photoanodes
Atomic layer deposited (ALD) “leaky” TiO 2 have gained interest as charge-selective protection layers for semiconductor solar fuel electrodes. Here we demonstrate the use of sputter-deposited TiO 2 layers as hole selective contacts for WO 3 /CuWO 4 type 2 heterojunction water oxidation photoanodes for the first time. TiO 2 protection layers with varying thicknesses (2 to 128 nm) were deposited using the RF magnetron sputtering technique. The resulting TiO 2 films are amorphous based on Raman spectroscopy and powder XRD. Photoelectrochemical scans and Vibrating Kelvin probe photovoltage spectroscopy show that 2-8 nm TiO 2 layers nearly double the photocurrent to 0.97 mA cm -2 under AM 1.5 illumination (19% AQE at 350 nm), increase the surface photovoltage signal by 25%, and increase the WO 3 /CuWO 4 bandgap. These effects can be attributed to the selectivity of TiO 2 for photoholes. Additionally, SPV data suggest that TiO 2 overlayers suppress copper-based surface recombination defects. Reduced photocurrent and the photovoltage are seen in thicker TiO 2 films (16 to 128 nm) as a result of an increasing hole transfer resistance and because of light shading effects according to photoaction spectra. The TiO 2 films also improve the stability of the WO 3 /CuWO 4 photoelectrodes, allowing nearly constant O 2 evolution over 3 hours after an initial 20-35% loss. Overall, this work establishes RF magnetron sputtering as a useful method to install amorphous TiO 2 passivation layers for improved WO 3 /CuWO 4 solar fuel photoelectrodes. Furthermore, we show how the combination of PEC with SPV measurements provides insight into the function of the TiO 2 coatings.
CuWO4↗
Exploring Local Vibrational Structure in Protein-Bound Chlorophyll a: Isotope-Enrichment Experiments and Electrostatic Analysis
Local chlorophyll (Chl) vibrations play an essential role in biological photosynthesis by facilitating rapid energy transfer between pigments. In research studies, they also provide a useful spectroscopic probe of the local protein environment that surrounds each pigment. However, measuring the complete vibrational absorption spectrum of a protein-bound Chl molecule is much more difficult than, for example, Chl in neat solvent due to overlap with protein vibrations that typically drown out Chl vibrational features. Resonance Raman and fluorescence spectroscopies provide a way around this problem for Franck–Condon active vibrations, but these often rely on cryogenic measurement conditions and fail to capture vibrational signatures from, e.g., ester-group vibrations that lack coupling to a convenient electronic transition. In the present contribution, we use 13 C-enrichment of the protein backbone to shift protein background signals to lower frequency, providing a largely clean spectral window in which to study local Chl a C═O stretch modes. A room-temperature absorption spectrum for Chl a in the water-soluble chlorophyll protein (WSCP) of Lepidium virginicum is thus extracted as a difference between protein-plus-pigment and protein-only vibrational spectra. Excellent agreement in the molecular fingerprint region with the vibrational spectrum of Chl a in organic solvents confirms that the resulting spectrum represents the response of the protein-bound Chl a molecule. Furthermore, the ester group resonance is observed to shift in response to the S53P mutation that eliminates a 17 3 ester group hydrogen bond from the protein environment. Finally, we analyze these experimental results using MD-based electrostatic analysis, finding that electric-field mapping at the C atom of the ester group provides a satisfactory explanation for the observed frequency shifts between organic solvent and protein environment. MD analysis further suggests that a red-shifted ester peak observed experimentally for the S53P mutant results from solvation of the 17 3 Chl ester group due increase water penetration into the Chl-binding pocket relative to wild-type WSCP. Here, we anticipate that these results will prove useful both for benchmarking future simulation work and as a reference for interpreting Chl vibrational spectra as a probe of pigment–protein interactions.
14 SOLAR ENERGY↗