Bayesian estimation of the hydroxyl radical diffusion coefficient at low temperature and high pressure from atomistic molecular dynamics
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Carter T. Butts↗
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Non-Additive Voltametric Currents From a Mixture of Two, Three and Four Redox-Active Compounds and Electroanalytical Implications
We have published recently the effect of dissimilar diffusion coefficients on the size of the voltammetric waves from a mixture of two redox-active compounds. Similarly, at the potential range where three redox-active species, decamethylferrocene (dMeFc), ferrocene (Fc) and N-methylphenothiazine (MePTZ), are oxidized simultaneously with rates controlled by linear diffusion, electrogenerated radicals diffusing outwards from the electrode react with the original species diffusing towards the electrode from the bulk; thus, Fc(+) reacts with dMeFc producing Fc and dMeFc(+), while MePTZ(+) reacts both with dMeFc producing MePTZ and dMeFc(+), and with Fc producing MePTZ and Fc(+). These reactions replace dMeFc with Fc at the second plateau, and both dMeFc and Fc with MePTZ at the third plateau. Since the diffusion coefficients of the three species are not equal, the mass-transfer limited currents of the second and the third oxidation wave plateaus change by approx. 10%. Numerical simulations of the experimental voltamograms support this mechanism. Similar results were also obtained for a mixture of four redoxactive compounds. The implications of this non-additive nature of currents on: (a) the use of internal voltammetric standards for quantitative analysis of a mixture of redox-active compounds; and, (b) the half wave potentials (E1/2) of the 2nd, 3rd and 4th waves for qualitative analysis, will be discussed.
Dass, Amala↗
In General, the Total Voltammetric Current from a Mixture of Redox-Active Substances will Not be the Sum of the Currents that Each Substance would Produce Independently at the Same Concentration as in the Mixture
At the potential range where both decamethylferrocene (dMeFc) and ferrocene (Fc) are oxidized with rates controlled by linear diffusion, electrogenerated Fc(+) radicals diffusing outwards from the electrode react quantitatively (K23 C=5.8 x 10(exp 8) with dMeFc diffusing towards the electrode and produce Fc and dMeFc. That reaction replaces dMeFc with Fc, whose diffusion coefficient is higher than that of dMeFc(+), and the total mass-transfer limited current from the mixture is increased by approximately 10%. Analogous observations are made when mass-transfer is controlled by convective-diffusion as in RDE voltammetry. Similar results have been obtained with another, and for all practical purposes randomly selected pair of redox-active substances, [Co(bipy)3](2+) and N - methylphenothiazine (MePTZ); reaction of MePTZ(+) with [Co(bipy)3](2+) replaces the latter with MePTZ, which diffuses faster and the current increases by approximately 20%. The experimental voltammograms have been simulated numerically and the role of (a) the rate constant of the homogeneous reaction; (b) the relative concentrations; and, (c) the diffusion coefficients of all species involved have been studied in detail. Importantly, it was also identified that within any given redox system the dependence of the mass-transfer limited current on the bulk concentrations of the redox-active species is expected to be non-linear. These findings are discussed in terms of their electroanalytical implications.
Leventis, Nicholas↗
The CN radical in diffuse interstellar clouds
A survey of 15 lines of sight for the CN B2Sigma(+) X2Sigma(+) interstellar absorption lines shows that the CN column density in diffuse interstellar clouds follows the relation log N(CN) is proportional to m log N(H2), where m is approximately equal to 3. This result is reproduced by a reaction network in which CN is produced primarily from C2 by the neutral-neutral reaction C2 + N yields CN + C, and photodissociation is the main destruction pathway for the neutral molecules CH, C2, and CN. The CN radical is the first molecular species observed in diffuse clouds that requires a neutral-neutral reaction for its formation in the gas phase. The network also reproduces the observed ratio N(CN)/N(H2).
Federman, S. R.↗
Spatiotemporal Reaction Dynamics Control in Two‐Photon Polymerization for Enhancing Writing Characteristics
Since 2001, 3D microfabrication based on two‐photon polymerization (TPP) has drawn extensive attention and interest in biology, optics, photonics, material science, and high‐energy physics. The in‐volume fabrication capability due to the threshold behavior of two‐photon absorption enables TPP higher flexibility compared with other nanofabrication techniques. However, as determined by the in‐volume fabrication feature as well as various reaction dynamics, the writing characteristics of TPP, such as throughput, accuracy, surface quality, and fabrication capability, are still limited. Herein, a comprehensive study is performed on the spatiotemporal behavior of reaction dynamics during TPP fabrication, mainly focusing on spatiotemporal characteristics of radical diffusion, photothermal effect, microscale mechanics, and voxel stacking process. Based on the study, a nonsequential fabrication method is established to simultaneously improve key writing characteristics of TPP and realize sharp features, high speeds, large overhang structure, and smooth surfaces. The method established in this work can be applied to improve the performance of functional devices for various fields.
36 MATERIALS SCIENCE↗
Composition, structure and chemistry of interstellar dust
The observational constraints on the composition of the interstellar dust are analyzed. The dust in the diffuse interstellar medium consists of a mixture of stardust (amorphous silicates, amorphous carbon, polycyclic aromatic hydrocarbons, and graphite) and interstellar medium dust (organic refractory material). Stardust seems to dominate in the local diffuse interstellar medium. Inside molecular clouds, however, icy grain mantles are also important. The structural differences between crystalline and amorphous materials, which lead to differences in the optical properties, are discussed. The astrophysical consequences are briefly examined. The physical principles of grain surface chemistry are discussed and applied to the formation of molecular hydrogen and icy grain mantles inside dense molecular clouds. Transformation of these icy grain mantles into the organic refractory dust component observed in the diffuse interstellar medium requires ultraviolet sources inside molecular clouds as well as radical diffusion promoted by transient heating of the mantle. The latter process also returns a considerable fraction of the molecules in the grain mantle to the gas phase.
Tielens, Alexander G. G. M.↗
Amorphous to Amorphous Form Transitions of Water Ice and Astrophysical Implications
We have combined Selected Area Electron Diffraction (SAED) and cryogenic techniques in an instrumental configuration that allows observing the structure of vapor deposited ice as it evolves during warmup. The ice is deposited in-situ inside an Hitachi H-500 H transmission electron microscope at a base pressure of 1-5 x 10(exp -7) torr on a thin amorphous carbon substrate at 15K or 86K and warmed up at a rate of 1-2 K/min. We find a progression of amorphous forms and well defined amorphous to amorphous transitions. Apart from the well known low-density form of ice, we confirm the presence of a high-density form and find a third amorphous form that coexists with cubic ice. We will report too on the amorphous to crystalline transition and the implications of these results for radical diffusion and gas retention observed in laboratory analog studies of interstellar and cometary ices.
Jenniskens, Peter↗
The C4H radical and the diffuse interstellar bands. An ab initio study
An ab initio study of the low-lying electronic states of C4H has been presented where the species studied has a chi(2)sigma(+) ground state and two low lying pi states. Based on the vertical and adiabatic excitation energies between those states it is suggested that the 4428 A diffuse interstellar band is not carried by C4H. The application of the particle in a box model shows strong coincidences between the strong DIB's and predicted wavelengths of pi-pi transitions in C(2n)H series. Based on those coincidences, it is suggested the C(2n)H species as good candidates for carriers of diffuse interstellar bands.
Kolbuszewski, Marcin↗
A Role of the Reaction Kernel in Propagation and Stabilization of Edge Diffusion Flames of C1-C3 Hydrocarbons
Diffusion flame stabilization is of essential importance in both Earth-bound combustion systems and spacecraft fire safety. Local extinction, re-ignition, and propagation processes may occur as a result of interactions between the flame zone and vortices or fire-extinguishing agents. By using a computational fluid dynamics code with a detailed chemistry model for methane combustion, the authors have revealed the chemical kinetic structure of the stabilizing region of both jet and flat-plate diffusion flames, predicted the flame stability limit, and proposed diffusion flame attachment and detachment mechanisms in normal and microgravity. Because of the unique geometry of the edge of diffusion flames, radical back-diffusion against the oxygen-rich entrainment dramatically enhanced chain reactions, thus forming a peak reactivity spot, i.e., reaction kernel, responsible for flame holding. The new results have been obtained for the edge diffusion flame propagation and attached flame structure using various C1-C3 hydrocarbons.
Takahashi, Fumiaki↗
Diffusion and Kinetics in Organic Radical Polymers
This final report describes the accomplishments, products, and participants on the project titled "Diffusion and Kinetics in Organic Radical Polymers", Award No DE-SC0014006.
36 MATERIALS SCIENCE↗
Probing soft X-ray induced photoreduction of a model Mn-complex at cryogenic conditions
Soft X-ray absorption spectroscopy of first row transition elements at their respective L -edges provides important information about the oxidation and spin states of the metal centers. However, the associated sample damage in radiation-sensitive samples substantially alters the electronic and chemical structures of redox-active metal centers. Here, we measure the soft X-ray spectrum of the model Mn III (acac) 3 complex containing a redox-active Mn III metal center in an octahedral environment with a superconducting transition-edge sensor detector. To reduce the secondary damage resulting primarily from the diffusion of radicals and electrons, the spectra are collected at 30 K and 80 K on solid samples. Starting from the first scan, we detect the contribution of X-ray induced sample damage leading to a change in the Mn II intensity. However, at low temperatures, particularly at 30 K, we do not observe a gradual increase in the radiation damage with successive scans with the X-ray beam at the same spot. At our estimated dose of 90 kGy, we find 62% of Mn III (acac) 3 is still intact at 30 K. However, at room temperature, we see a gradual increase in radiation damage with increasing numbers of scans at the same spot, which is consistent with the possibility of increased diffusion rates of secondary radicals and electrons as noted in other studies.
L-edge spectroscopy↗
The effects of complex chemistry on triple flames
The structure, ignition, and stabilization mechanisms for a methanol (CH3OH)-air triple flame are studied using Direct Numerical Simulations (DNS). The methanol (CH3OH)-air triple flame is found to burn with an asymmetric shape due to the different chemical and transport processes characterizing the mixture. The excess fuel, methanol (CH3OH), on the rich premixed flame branch is replaced by more stable fuels CO and H2, which burn at the diffusion flame. On the lean premixed flame side, a higher concentration of O2 leaks through to the diffusion flame. The general structure of the triple point features the contribution of both differential diffusion of radicals and heat. A mixture fraction-temperature phase plane description of the triple flame structure is proposed to highlight some interesting features in partially premixed combustion. The effects of differential diffusion at the triple point add to the contribution of hydrodynamic effects in the stabilization of the triple flame. Differential diffusion effects are measured using two methods: a direct computation using diffusion velocities and an indirect computation based on the difference between the normalized mixture fractions of C and H. The mixture fraction approach does not clearly identify the effects of differential diffusion, in particular at the curved triple point, because of ambiguities in the contribution of carbon and hydrogen atoms' carrying species.
Echekki, T.↗
Probing the electronic structure and spectroscopy of pyrrolyl and imidazolyl radicals using high-resolution photoelectron imaging of cryogenically cooled anions
High-resolution photoelectron imaging and photodetachment spectroscopy of cryogenically cooled pyrrolide and imidazolide anions are used to probe the electronic structure and spectroscopy of pyrrolyl and imidazolyl radicals. The high-resolution data allow the ground state vibronic structures of the two radicals to be completely resolved, yielding accurate electron affinities of 2.1433 ± 0.0008 eV and 2.6046 ± 0.0006 eV for pyrrolyl and imidazolyl radicals, respectively. Fundamental frequencies for eight vibrational modes of pyrrolyl and ten vibrational modes of imidazolyl are measured, including several nonsymmetric Franck–Condon-forbidden modes. Two electronic excited states are also observed for the two radicals, displaying diffuse spectral features in both systems. The observations of nonsymmetric vibrational modes in the ground states and the diffuse excited state features provide strong evidence for vibronic couplings between the ground state and the two close-by excited states. The 2-pyrrolide isomer is also observed as a minor species from the electrospray ionization source and the electron affinity of 2-pyrrolyl is measured to be 1.6690 ± 0.0030 eV along with five vibrational frequencies. Even though the HOMOs of both pyrrolide and imidazolide anions are p orbitals, photodetachment spectroscopy reveals completely different threshold behaviors for the two anions: a d-wave-dominated spectrum for pyrrolide and an s-wave-dominated spectrum for imidazolide. Furthermore, the current study provides a wealth of electronic and spectroscopic information, which is ideal to compare with more accurate vibronic coupling calculations for these two important radicals, as well as interesting information about the photodetachment dynamics of the two anions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
4D-STEM of Beam-Sensitive Materials
We report that a scanning electron nanobeam diffraction, or 4D-STEM (four-dimensional scanning transmission electron microscopy), is a flexible and powerful approach to elucidate structure from "soft" materials that are challenging to image in the transmission electron microscope because their structure is easily damaged by the electron beam. In a 4D-STEM experiment, a converged electron beam is scanned across the sample, and a pixelated camera records a diffraction pattern at each scan position. This four-dimensional data set can be mined for various analyses, producing maps of local crystal orientation, structural distortions, crystallinity, or different structural classes. Holding the sample at cryogenic temperatures minimizes diffusion of radicals and the resulting damage and disorder caused by the electron beam. The total fluence of incident electrons can easily be controlled during 4D-STEM experiments by careful use of the beam blanker, steering of the localized electron dose, and by minimizing the fluence in the convergent beam thus minimizing beam damage. This technique can be applied to both organic and inorganic materials that are known to be beam-sensitive; they can be highly crystalline, semicrystalline, mixed phase, or amorphous. One common example is the case for many organic materials that have a π-π stacking of polymer chains or rings on the order of 3.4-4.2 Å separation. If these chains or rings are aligned in some regions, they will produce distinct diffraction spots (as would other crystalline spacings in this range), though they may be weak or diffuse for disordered or weakly scattering materials. We can reconstruct the orientation of the π-π stacking, the degree of π-π stacking in the sample, and the domain size of the aligned regions. This Account summarizes illumination conditions and experimental parameters for 4D-STEM experiments with the goal of producing images of structural features for materials that are beam-sensitive. We will discuss experimental parameters including sample cooling, probe size and shape, fluence, and cameras. 4D-STEM has been applied to a variety of materials, not only as an advanced technique for model systems, but as a technique for the beginning microscopist to answer materials science questions. It is noteworthy that the experimental data acquisition does not require an aberration-corrected TEM but can be produced on a variety of instruments with the right attention to experimental parameters.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Gamma radiation-induced defects in KCl, MgCl 2 , and ZnCl 2 salts at room temperature
Room temperature post-irradiation measurements of diffuse reflectance and electron paramagnetic resonance spectroscopies were made to characterize the long-lived radiation-induced species formed from the gamma irradiation of solid KCl, MgCl 2 , and ZnCl 2 salts up to 100 kGy. The method used showed results consistent with those reported for electron and gamma irradiation of KCl in single crystals. Thermal bleaching of irradiated KCl demonstrated accelerated disaggregation of defect clusters above 400 K, due to decomposition of Cl 3 - . The defects formed in irradiated MgCl 2 comprised a mixture of Cl 3 - , F-centers, and Mg + associated as M-centers. Further, Mg metal cluster formation was also observed at 100 kGy, in addition to accelerated destruction of F-centers above 20 kGy. Irradiated ZnCl 2 afforded the formation of Cl 2 - due to its high ionization potential and crystalline structure, which decreases recombination. The presence of aggregates in all cases indicates the high diffusion of radicals and the predominance of secondary processes at 295 K. Additionally, thermal bleaching studies showed that chloride aggregates’ stability increases with the ionization potential of the cation present. The characterization of long-lived radiolytic transients of pure salts provides important information for the understanding of complex salt mixtures under the action of gamma radiation.
36 MATERIALS SCIENCE↗
Nitric Oxide Production from Nitrite plus Ascorbate during Ischemia upon Hippocampal Glutamate NMDA Receptor Stimulation
Nitric oxide (•NO), a diffusible free radical, is an intercellular messenger, playing a crucial role in several key brain physiological processes, including in neurovascular coupling (NVC). In the brain, glutamatergic activation of the neuronal nitric oxide synthase (nNOS) enzyme constitutes its main synthesis pathway. However, when oxygen (O2) supply is compromised, such as in stroke, ischemia, and aging, such •NO production pathway may be seriously impaired. In this context, evidence suggests that, as already observed in the gastric compartment, the reduction of nitrite by dietary compounds (such as ascorbate and polyphenols) or by specific enzymes may occur in the brain, constituting an important rescuing or complementary mechanism of •NO production. Here, using microsensors selective for •NO, we show that nitrite enhanced the •NO production in a concentration-dependent manner and in the presence of ascorbate evoked by N-methyl-D-aspartate (NMDA) and glutamate stimulation of rat hippocampal slices. Additionally, nitrite potentiated the •NO production induced by oxygen-glucose deprivation (OGD). Overall, these observations support the notion of a redox interaction of ascorbate with nitrite yielding •NO upon neuronal glutamatergic activation and given the critical role of NO as the direct mediator of neurovascular coupling may represents a key physiological mechanism by which •NO production for cerebral blood flow (CBF) responses to neuronal activation is sustained under hypoxic/acidic conditions in the brain.
Nunes, Carla (ORCID:0000000274521592)↗
Laser-saturated fluorescence measurements in laminar sooting diffusion flames
The hydroxyl radical is known to be one of the most important intermediate species in the combustion processes. The hydroxyl radical has also been considered a dominant oxidizer of soot particles in flames. In this investigation the hydroxyl concentration profiles in sooting diffusion flames were measured by the laser-saturated fluorescence (LSF) method. The temperature distributions in the flames were measured by the two-line LSF technique and by thermocouple. In the sooting region the OH fluorescence was too weak to make accurate temperature measurements. The hydroxyl fluorescence profiles for all four flames presented herein show that the OH fluorescence intensities peaked near the flame front. The OH fluorescence intensity dropped sharply toward the dark region of the flame and continued declining to the sooting region. The OH fluorescence profiles also indicate that the OH fluorescence decreased with increasing height in the flames for all flames investigated. Varying the oxidizer composition resulted in a corresponding variation in the maximum OH concentration and the flame temperature. Furthermore, it appears that the maximum OH concentration for each flame increased with increasing flame temperature.
Wey, Changlie↗
Symmetry‐Breaking Strategy Yields Dopant‐Free Small Molecule Hole Transport Materials for Inorganic Perovskite Solar Cells with 20.58% Efficiency and Outstanding Stability
Abstract Inorganic perovskites are known for their excellent photothermal stability; however, the photothermal stability of all‐inorganic n‐i‐p perovskite solar cells (PSCs) is compromised due to ion diffusion and free radical‐induced degradation caused by the use of doped spiro‐OMeTAD hole transport materials (HTMs). In this study, two isomeric donor–acceptor–donor (D–A–D) type small molecules, namely HBT and HiBT, were developed and used as dopant‐free HTMs, using 2,1,3‐benzothiadiazole or benzo[d][1,2,3]thiadiazole as acceptor moieties. The HiBT molecule, with its symmetry‐breaking features, exhibits a large dipole moment, enhanced coordination‐active sites, and a well‐aligned energy level structure, all of which contribute to passivating perovskite surface defects and improving free charge separation. As a result, inorganic CsPbI 3 PSCs with HiBT HTM achieved an impressive power conversion efficiency (PCE) of 20.58%, the highest reported for dopant‐free HTM‐based inorganic PSCs. Moreover, the enhanced hydrophobic properties of HiBT molecules, coupled with their ability to passivate perovskite surface defects, contribute to significantly improved device stability. The unencapsulated devices based on HiBT HTM retained over 83% and 80% of their initial efficiency after being stored at 85 °C for 50 days and undergoing maximum power point (MPP) tracking at 85 °C for 1100 h, respectively. These results highlight that the symmetry‐breaking strategy is an exceptionally effective approach for designing efficient, dopant‐free small molecule HTMs, significantly contributing to both the high efficiency and enhanced stability of all‐inorganic PSCs.
Chemistry↗