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At least 1,423 records · Page 79
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

A Chemical Understanding of the Band Convergence in Thermoelectric CoSb 3 Skutterudites: Influence of Electron Population, Local Thermal Expansion, and Bonding Interactions

N-Type skutterudites, such as Yb x Co 4 Sb 12 , have recently been shown to exhibit high valley degeneracy with possible band convergence, explaining the excellent thermoelectric efficiency of these materials. Using a combined theoretical and experimental approach involving temperature-dependent synchrotron diffraction, molecular orbital diagrams, and computational studies, the chemical nature of critical features in the band structure is highlighted. We identify how n-type doping on the filler site induces structural changes that are observed in both the diffraction data and computational results. Additionally, we show how chemical n-type doping slightly alters the electronic band structure, moving the high-valley degeneracy secondary conduction band closer to the primary conduction band and thus inducing band convergence.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Nuclear Quantum Effects in Water and Aqueous Systems: Experiment, Theory, and Current Challenges

Nuclear quantum effects influence the structure and dynamics of hydrogen bonded systems, such as water, which impacts their observed properties with widely varying magnitudes. This review highlights the recent significant developments in the experiment, theory and simulation of nuclear quantum effects in water. Novel experimental techniques, such as deep inelastic neutron scattering, now provide a detailed view of the role of nuclear quantum effects in water’s properties. These have been combined with theoretical developments such as the introduction of the competing quantum effects principle that allows the subtle interplay of water’s quantum effects and their manifestation in experimental observables to be explained. We discuss how this principle has recently been used to explain the apparent dichotomy in water’s isotope effects, which can range from very large to almost nonexistent depending on the property and conditions. We then review the latest major developments in simulation algorithms and theory that have enabled the efficient inclusion of nuclear quantum effects in molecular simulations, permitting their combination with on-the-fly evaluation of the potential energy surface using electronic structure theory. Finally, we identify current challenges and future opportunities in the area.

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

Comparison of the Chemical Composition of Liquids from the Pyrolysis and Hydrothermal Liquefaction of Lignocellulosic Materials

Major differences in thermal stability and hydrotreatment behavior of HTL and pyrolysis oils have been reported in the literature. However, little is known about the variations in the chemical composition of these oils that could explain such differences. Two commercial wood pyrolysis oils (Pyrovac and BTG), and their water-soluble (WS) and water-insoluble fractions (WIS) were analyzed and compared with the aqueous (WS WD-57 ) and oily (WIS WS-57 ) fractions obtained from hydrothermal liquefaction (HTL) of Douglas-fir. The samples were characterized by GC/MS, Karl Fischer titration, carbonyl content, total acid number, elemental composition, calorific value, proximate analysis, Fourier Transform Infrared Spectroscopy (FTIR), Folin-Ciocalteu (FC), and UV fluorescence. All the fractions were also analyzed by Fourier Transform Ion Cyclotron Resonance Mass Spectroscopy (FT-ICR-MS) and by Electrospray Ionization (EI). The most prevalent class of compounds in the water insoluble phases were phenols derived from lignin. Water-soluble phases contain mostly the oxygenated compounds derived from cellulose and hemicellulose and were richer in carbonyl functional groups. The water content of the resulting aqueous phases were between: 65 (WS BTG ) and 96 (WS Pyrovac ) wt. %. The bio-oil from BTG has higher water content and lower HHV, compared to Pyrovac oil. The GC/MS results of BTG oil show the presence of a more prominent acetic acid peak and higher TAN number than the Pyrovac oil. The GC/MS of Pyrovac oil showed more obvious mono-phenol peaks. The quantification of this family by Folin-Ciocalteu method confirmed higher content of monophenolic compounds compared with the BTG oil. The lower thermal stability of pyrolysis oils compared with HTL biocrudes can be partially explained by the fact that pyrolysis oils (BTG and Pyrovac) contain carbohydrates while HTL biocrude (WIS WD-57 ) doesn’t. Thus, we decided to further investigate the chemical differences between the phenolic rich fractions insoluble in water and the holocellulose derived compounds soluble in water. Even after water extraction, the acid content of the water insoluble fraction from BTG (WISBTG) was higher than the acid content of the water insoluble fraction obtained by HTL (WISWSD-57). Likewise, the acid content of the aqueous phases derived from pyrolysis oils (WS Pyrovac , WS BTG ) was also higher than for the aqueous phase obtained by HTL (WSWSD-57). This result is in part due to the use of bases in the HTL process that neutralizes the acid formed in that process. Moreover, the starting feedstock may also influence the differences between the oils. Although, the UV-Fluorescence spectra, ICR-MS and the EI analyses showed some minor differences in the molecular weight and chemical make-up of the oligomers soluble and insoluble in water from pyrolysis and HTL; the differences observed were not large enough to justify the differences in behavior between these oils reported in the literature. Our results suggest that the differences observed between HTL biocrudes and pyrolysis oils are likely partially due to the presence of holocellulose derived products in the pyrolysis oils and higher acid contents.

09 BIOMASS FUELS↗
DOE OSTI2017

Evolution of Functional Groups during Pyrolysis Oil Upgrading

In this paper, we examine the evolution of functional groups (carbonyl, carboxyl, phenol, and hydroxyl) during stabilization at 100–200 °C of two typical wood derived pyrolysis oils from BTG and Amaron in a batch reactor over Ru/C catalyst for 4h. An aqueous and an oily phase were obtained. The content of functional groups in both phases were analyzed by GC/MS, 31P-NMR, 1H-NMR, elemental analysis, KF titration, carbonyl groups by Faix, Folin – Ciocalteu method and UV-Fluorescence. The consumption of hydrogen was between 0.007 and 0.016 g/g oil, and 0.001-0.020 g of CH4/g of oil, 0.005-0.016 g of CO2/g oil and 0.03-0.10 g H2O/g oil were formed. The content of carbonyl, hydroxyl, and carboxyl groups in the volatile GC-MS detectable fraction decreased (80, 65, and ~70% respectively), while their behavior in the total oil and hence in the non-volatile fraction was more complex. The carbonyl groups initially decreased having minimum at ~125-150°C and then increased, while the hydroxyl groups had reversed trend. This might be explained by initial hydrogenation of the carbonyl groups to form hydroxyls, followed by continued dehydration reactions at higher temperatures that may increase their content. The 31P-NMR was on the limit of its sensitivity for the carboxylic groups to precisely detect changes in the non-volatile fraction, however the more precise titration method showed that the concentration of carboxylic groups in the non-volatile fraction remains constant with increased stabilization temperature. The UV-Fluorescence results show that repolymerization increases with temperature. ATR-FTIR method coupled with deconvolution of the region between 1490 and 1850 cm-1 showed to be a good tool for following the changes in carbonyl groups and phenols of the stabilized pyrolysis oils. The deconvolution of the IR bands around 1050 and 1260 cm-1 correlated very well with the changes in the 31P-NMR silent O groups (likely ethers). Most of the H2O formation could be explained from the significant reduction of these silent O groups (from 12% in the fresh oils, to 6 to 2% in the stabilized oils) most probably belonging to ethers.

Stankovikj, Filip↗
DOE OSTI2024

A Detailed Reaction Mechanism for Thiosulfate Oxidation by Ozone in Aqueous Environments

The ozone oxidation, or ozonation, of thiosulfate is an important reaction for wastewater processing, where it is used for remediation of mining effluents, and for studying aerosol chemistry, where its fast reaction rate makes it an excellent model reaction. Although thiosulfate ozonation has been studied since the 1950s, challenges remain in developing a realistic reaction mechanism that can satisfactorily account for all observed products with a sequence of elementary reaction steps. Here, we present novel measurements using trapped microdroplets to study the pH-dependent thiosulfate ozonation kinetics. We detect known products and intermediates, including SO32-, SO42-, S3O62-, and S4O62-, establishing agreement with the literature. However, we identify S2O42- as a new reaction intermediate and find that the currently accepted mechanism does not directly explain observed pH effects. Thus, we develop a new mechanism, which incorporates S2O42- as an intermediate and uses elementary steps to explain the pH dependence of thiosulfate ozonation. The proposed mechanism is tested using a kinetic model benchmarked to the experiments presented here, then compared to literature data. We demonstrate good agreement between the proposed thiosulfate ozonation mechanism and experiments, suggesting that the insights in this paper can be leveraged in wastewater treatment and in understanding potential climate impacts.

Deal, Alexandra M↗
DOE OSTI2025

Integrating Contaminant Source Indicators, Water Quality Measures, and Ecotoxicity to Characterize Contaminant Mixtures and Per- and Polyfluoroalkyl Substance (PFAS) Variability in an Urban Watershed

Thousands of chemical contaminants threaten watersheds but are time and cost prohibitive to monitor. Identifying their sources, transport, and ecological risk is limited in heterogeneous urban watersheds. We present an integrative watershed approach using source-specific indicator compounds, common water quality measures, and ecotoxicity assays to examine the distribution of contaminant mixtures in an urbanized watershed. Indicator compound concentrations were temporally and spatially distributed for treated/untreated sewage (sucralose, artificial sweetener), road runoff (diphenyl-guanidine [DPG] and 6PPD-quinone [6PPD-Q], automobile tire additives), and lawncare runoff (aminomethanephosphonic acid (AMPA), major degradant of the herbicide glyphosate). Sucralose was predominately sourced from treated wastewater; measurable concentrations in tributaries indicated raw sewage inputs. DPG and 6PPD-Q concentrations correlated to road density during base flow and were elevated during stormflow. AMPA was measurable spring through fall, especially where lawns were dense. When specific sources dominated flow, water quality measures correlated with wastewater (sulfate, potassium, chloride, and sodium) and road runoff (chromium and lead) indicators. The limited behavioral toxicity observed in exposed zebrafish (Danio rerio) (18%) was not well explained by source-indicators. PFAS concentrations were highly variable spatially but not well explained by our source-specific indicator compounds. Here, more costly compound-specific monitoring may be necessary when multiple sources exist or when unexpected toxicity trends occur.

computer simulations↗
DOE OSTI2016

Rupturing of Biological Spores As a Source of Secondary Particles in Amazonia

Airborne biological particles, such as fungal spores and pollen, are ubiquitous in the Earth’s atmosphere and play an important role in the atmospheric environment and climate, impacting air quality, cloud formation, and the Earth’s radiation budget. The atmospheric transformations of airborne biological spores at elevated relative humidity remain poorly understood and their climatic role is uncertain. Using an environmental scanning electron microscope (ESEM), we observed rupturing of Amazonian fungal spores and subsequent release of nanometer to submicron size fragments after exposure to high humidity. We find that fungal fragments contain elements of inorganic salts (e.g., Na and Cl). They are hygroscopic in nature with a growth factor up to 2.3 at 96% relative humidity, thus they may potentially influence cloud formation. Due to their hygroscopic growth, light scattering cross sections of the fragments are enhanced by up to a factor of 10. Furthermore, rupturing of fungal spores at high humidity may explain the bursting events of nanoparticles and may provide insight into new particle formation in Amazonia.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2017

Dynamic Succession of Groundwater Sulfate-Reducing Communities during Prolonged Reduction of Uranium in a Contaminated Aquifer

To further understand the diversity and dynamics of SRB in response to substrate amendment, we sequenced genes coding for the dissimilatory sulfite reductase (dsrA) in groundwater samples collected after an emulsified vegetable oil (EVO) amendment, which sustained U(VI)-reducing conditions for one year in a fast-flowing aquifer. EVO amendment significantly altered the composition of groundwater SRB communities. Sequences having no closely related-described species dominated (80%) the indigenous SRB communities in nonamended wells. After EVO amendment, Desulfococcus , Desulfobacterium , and Desulfovibrio , known for long-chain-fatty-acid, short-chain-fatty-acid and H 2 oxidation and U(VI) reduction, became dominant accounting for 7 ± 2%, 21 ± 8%, and 55 ± 8% of the SRB communities, respectively. Succession of these SRB at different bioactivity stages based on redox substrates/products (acetate, SO 4 –2 , U(VI), NO 3 – , Fe(II), and Mn(II)) was observed. Desulfovibrio and Desulfococcus dominated SRB communities at 4–31 days, whereas Desulfobacterium became dominant at 80–140 days. By the end of the experiment (day 269), the abundance of these SRB decreased but the overall diversity of groundwater SRB was still higher than non-EVO controls. Up to 62% of the SRB community changes could be explained by groundwater geochemical variables, including those redox substrates/products. A significant ( P < 0.001) correlation was observed between groundwater U(VI) concentrations and Desulfovibrio abundance. Lastly, our results showed that the members of SRB and their dynamics were correlated significantly with slow EVO biodegradation, electron donor production and maintenance of U(VI)-reducing conditions in the aquifer.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Direct Exchange Mechanism for Interlayer Ions in Non-Swelling Clays

The mobility of radiocesium in the environment is largely mediated by cation exchange in micaceous clays, in particular Illite—a non-swelling clay mineral that naturally contains interlayer K + and has high affinity for Cs + . Although exchange of interlayer K + for Cs + is nearly thermodynamically nonselective, recent experiments show that direct, anhydrous Cs + -K + exchange is kinetically viable and leads to the formation of phase-separated interlayers through a mechanism that remains unclear. Here, using classical atomistic simulations and density functional theory calculations, we identify a molecular-scale positive feedback mechanism in which exchange of the larger Cs + for the smaller K + significantly lowers the migration barrier of neighboring K + , allowing exchange to propagate rapidly once initiated at the clay edge. Barrier lowering upon slight increase in layer spacing (~0.7 Å) during Cs + exchange is an example of “chemical-mechanical coupling” that likely explains the observed sharp exchange fronts leading to interstratification. Interestingly, we find that these features are thermodynamically favored even in the absence of a heterogeneous layer charge distribution.

Ruiz Pestana, Luis↗
DOE OSTI2017

Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields

We report chamber measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation, where radical concentrations were systematically varied and the molecular composition of semi to low volatility gases and SOA were measured online. Using a detailed chemical mechanism, we find that to explain the behavior of low volatility products and SOA mass yields relative to input H2O2 concentrations, the second generation dihydroxy hydroperoxy peroxy radical (C5H11O6•) must undergo an intra-molecular H-shift with a net forward rate constant of order 0.1 s-1 or higher, consistent with quantum chemical calculations which suggest a net forward rate constant of 0.3-0.9 s-1. Furthermore, these calculations suggest the dominant product of this isomerization is a dihydroxy hydroperoxy epoxide (C5H10O5) which is expected to have a saturation vapor pressure ~2 orders of magnitude higher than the dihydroxy dihydroperoxide, ISOP(OOH)2 (C5H12O6), a major product of the peroxy radical reacting with HO2. These results provide strong constraints on the likely volatility distribution of isoprene oxidation products under atmospheric conditions and thus on the importance of non-reactive gas-particle partitioning of isoprene oxidation products as an SOA source.

D’Ambro, Emma L. (ORCID:0000000230419027)↗
DOE OSTI2017

Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol

Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution dynamics are poorly understood. In this article, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversibly reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Unified View of the Local Cation-Ordered State in Inverse Spinel Oxides

Cation ordering/disordering in spinel oxides plays a necessary role in the rich physical and chemical properties which are hallmarks of the structural archetype. A variety of cation-ordering motifs have been reported for spinel oxides with multiple cations residing on the octahedral site (or B-site). This has attracted tremendous attention from both experimental and theoretical communities in the last few decades. Yet, no unified view has been reached, presumably due to the richness of cation species and corresponding complex arrangements emergent in this large family of compounds. Here, local cation-ordered ground states of (inverse) spinel oxides with two different cations on the octahedral site have been thoroughly investigated using neutron and X-ray total scattering, and a comprehensive theory has been proposed to explain the commonly observed cation-ordered polymorphs. It is found that a cation-zigzag-ordered structure (space group P4122) is the ground state for inverse spinel oxides with a pure or strong ionic lattice, while a cation-linear-ordered arrangement (space group Imma) emerges when one of the B-site cations forms very strong directional covalent bonds with lattice oxygen. The degree and length scale of cation ordering is strongly correlated with the charge and ionic radius difference between the two octahedral site cations. More complicated cation ordering schemes can be formed when there is a concomitant charge and orbital ordering which fall on a similar energy scale. This can lead to the formation of orbital-driven cation clusters or the broad concept of “molecules” in solid- state compounds. It is anticipated these findings will help to better understand the observed physical properties of spinel oxides and thus facilitate design strategies for improved functional materials.

25 ENERGY STORAGE↗
DOE OSTI2020

Practical considerations for atomistic structure modeling with Cryo-EM maps

We present our experiences and opinions with selected software with respect to atomistic structure modeling with single particle analysis derived maps. These are atomistic model building and fitting method selection criteria and implementation procedures. Since we explain common concepts and caveats that we have explained to our collaborators, we hope that this short perspective will help facilitate active discussion between scientists at different levels and backgrounds.

Kim, Doo Nam↗
DOE OSTI2025

Energetic and Electronic Properties of AcX and LaX (X = O and F)

The bonding and spectroscopic properties of LaX and AcX (X = O and F) diatomic molecules were studied by highlevel ab initio CCSD(T) and SO-CASPT2 electronic structure calculations. Bond dissociation energies (BDEs) were calculated at the Feller−Peterson−Dixon (FPD) level. Potential energy curves and spectroscopic constants for the lowest-lying spin−orbit Ω states were obtained at the SO-CASPT2/aQ-DK level. A dense manifold of excited states was described for the monofluorides with the ground states well separated from the excited states. The spectroscopic parameters were in good agreement with those reported experimentally for LaO and LaF. For the diatomic molecules containing actinides, no experimental data of these parameters was found, but the results were consistent with other high-level calculations. The BDEs calculated at the FPD level were 791.3 (LaO), 705.2 (AcO), 650.0 (LaF), and 678.6 (AcF) kJ/ mol. The NBO analysis showed that the monofluorides are essentially ionic, which explains why the BDE(AcF) is higher than BDE(LaF); for the monoxides, covalent contributions involving the d orbitals of the metal and the p orbitals of the oxygen are stronger for LaO than AcO, which explains the higher BDE for LaO. Finally, the bond orders are predicted to be 2 for LaF and AcF, 3 for AcO, and higher than 3 for LaO.

Basis sets↗
DOE OSTI2025

Modeling Pb(II) Adsorption on Mineral Surfaces: Bridging Density Functional Theory and Experiment with Thermodynamic Insights

Despite decades of work on aqueous lead (Pb) adsorption on a-Fe2O3 (hematite) and a-Al2O3 (alumina), gaps between measurements and modeling obscure molecular-level understanding. Achieving well-matched geometries between theory and experimental for mineral-water interfaces is a hurdle, as surface functional group type and distribution must be accounted for in determining mechanisms. Additionally, computational methods that can describe the substrate are often not appropriate to capture aqueous effects. Progress requires focusing on well-studied and relevant systems, such as key facets (001),(012), and (110) of hematite and alumina, and ubiquitous contaminants such as aqueous Pb. In the past, bulk-parametrized bond-valence principles were used to rationalize Pb(II) adsorption trends. These approaches can break down at surfaces, where flexible bonding environments and adsorption-induced surface relaxations play a critical role. Here, we adapt and apply a density functional theory (DFT) and thermodynamics framework, integrating DFT-calculated energies with experimental data and electrochemical principles, to predict Pb(II) adsorption. Our model results capture trends across the full set of surfaces and predict that inner-sphere Pb(II) sorption on (001) alumina varies from unfavorable to weakly favorable across a range of pH conditions. This aligns with experiment insights that Pb(II) interacts at that surface through outer-sphere interactions. Extending to Fe(II) adsorption, we demonstrate a coverage-dependent site preference, potentially explaining disorder in overlayers grown by the oxidative adsorption of Fe(II) on hematite (001).

lead contamination↗
DOE OSTI2017

Collapse Precedes Folding in Denaturant-Dependent Assembly of Ubiquitin

The folding of small protein ubiquitin (Ub), which plays an indispensable role in targeting proteins for degradation and DNA damage response, is complex. A number of experiments on Ub folding have reached differing conclusions regarding the relation between collapse and folding, and whether intermediates are populated. In order to resolve these vexing issues, we elucidate the denaturant-dependent thermodynamics and kinetics of Ub folding at low and neutral pH as a function of guanidinium chloride and urea using coarse-grained molecular simulations. The changes in the fraction of the folded Ub, and the radius of gyration (R g ) as a function of the denaturant concentration, [C], are in quantitative agreement with experiments. Under conditions used in experiments, R g of the unfolded state at neutral pH changes only by ≈17% as the [GdmCl] decreases from 6 to 0 M. We predict that the extent of compaction of the unfolded state increases as temperature decreases. A two-dimensional folding landscape as a function of R g and a measure of similarity to the folded state reveals unambiguously that the native state assembly is preceded by collapse, as discovered in fast mixing experiments on several proteins. Assessment of the folding trajectories, under mildly denaturing conditions ([GdmCl] = 1.0 M or [Urea] = 1.0 M), shows that Ub folds by collision between preformed secondary structural elements involving kinetic intermediates that are primarily stabilized by long-range contacts. Here, we explain the results of small angle X-ray scattering (SAXS) experiments on Ub quantitatively, and establishes that evolved globular proteins in the unfolded ensemble are poised to collapse as the solvent conditions for the biopolymer changes from good solvent to Θ-solvent like conditions on denaturant dilution. In the process, we explain the discrepancy between SAXS and single molecule fluorescent resonant energy transfer (smFRET) experiments, which have arrived at a contradicting conclusion concerning the collapse of polypeptide chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Dynamics of Quaternary Structure Transitions in R-State Carbonmonoxyhemoglobin Unveiled in Time-Resolved X-ray Scattering Patterns Following a Temperature Jump

It is well-known that tetrameric hemoglobin binds ligands cooperatively by undergoing a ligand-induced T → R quaternary structure transition, a structure-function relationship that has long served as a model system for understanding allostery in proteins. However, kinetic studies of the reverse, R → T quaternary structure transition following photolysis of carbonmonoxyhemoglobin (HbCO) reveal complex behavior that may be better explained by the presence of two different R quaternary structures coexisting in thermal equilibrium. Indeed, we report here time-resolved small- and wide-angle X-ray scattering (SAXS/WAXS) patterns of HbCO following a temperature jump that not only provide unambiguous evidence for more than one R state, but also unveil the time scale for interconversion between them. Since the time scale for the photolysis-induced R → T transition is likely different for different R-states, this structural heterogeneity must be accounted for to properly explain the kinetic heterogeneity observed in time-resolved spectroscopic studies following photolysis of HbCO.

Cho, Hyun Sun↗
DOE OSTI2020

Surface Enhanced Raman Scattering Selectivity in Proteins Arises from Electron Capture and Resonant Enhancement of Radical Species

Plasmon-enhanced Raman scattering is a powerful approach to detecting and characterizing proteins in live and dynamic biological systems. However, the selective detection/enhancement of specific residues as well as spectral diffusion and fluctuations have complicated the interpretation of enhanced Raman spectra and images of biological matter. In this paper, we therefore demonstrate that the amino acid tryptophan (Trp) can capture an electron from an excited plasmon, which generates a radical anion that is resonantly enhanced: a visible excited electronic state slides into resonance upon charging. This surface enhanced resonance Raman scattering (SERRS) mechanism explains the persistence of Trp signatures in the SERS and TERS spectra of proteins. Evidence for this picture includes the observation of visible resonances in the UV-Vis extinction spectrum, changes in the ground state vibrational spectrum, and plasmon-resonance dependent behavior. DFT calculations support the experimental observations. The behavior observed from the free Trp molecule is shown to explain the SERS spectrum of the Trp-cage protein. In effect, resonant Raman scattering from radicals formed through plasmonic excitation represents an under-investigated mechanism that may be exploited for chemical sensing applications. This work was supported by the National Institutes of Health Award R01-GM109988. The authors thank Hannah Shafaat for helpful discussions and providing an azurin sample for comparison. The authors also thank Joel Harris for providing constructive comments on our manuscript.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗