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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Direct measurements of channel specific rate constants in OH + C 3 H 8 illuminates prompt dissociations of propyl radicals

OH + molecules are an important class of reactions in combustion and atmospheric chemistry. Consequently, numerous studies have measured rate constants for these processes over an extended temperature range. A large majority of these experimental studies have utilized the decay of [OH] profiles (monitored either by absorption or laser-induced fluorescence) to obtain total rate constants. However, there are limited direct measurements of channel specific rate constants in this important class of reactions, particularly at combustion relevant temperatures. In the present experiments, we have directly measured site-specific rate constants for abstraction of the secondary C–H bond in OH + C 3 H 8 at high temperatures. Atomic resonance absorption spectrometry (ARAS) was used to monitor the formation of H-atoms from shock-heated mixtures of tert-butylhydroperoxide and C 3 H 8 at high temperatures. Simulations for the experimental H-atom profiles are sensitive only to abstraction of the secondary C–H bond leading to unambiguous measurements of the rate constants for this reaction. Over the T-range, 921 K < T < 1146 K, rate constants from the present experiments for OH + C 3 H 8 →H 2 O + i-C 3 H 7 can be represented by the Arrhenius expression, k = (3.935 ± 1.387) × 10-11 exp(-1681 ± 362 K/T )cm 3 molecule -1 s -1 Simulations of the lower temperature data (T < 1000 K) indicate that the H-atom profiles are also influenced to a minor extent by the thermal dissociation of iso-propyl, i-C 3 H 7 →H + C 3 H 6 , at short time-scales.

Shock Tube, H-ARAS, Prompt Dissociation, Bimolecul↗
DOE OSTI2017

Rate constants for H abstraction from benzo(a)pyrene and chrysene: a theoretical study

Density functional B3LYP/6-31G(d) and ab initio G3(MP2,CC) calculations have been carried out to determine thermal rate constants of direct H abstraction reactions from four- and five-ring polycyclic aromatic hydrocarbons (PAH) chrysene and benzo[a]pyrene by various radicals abundant in combustion flames, such as H, CH 3 , C 3 H 3 , and OH, using transition state theory. The results show that the H abstraction reactions with OH have the lowest barriers of ~4 kcal mol -1 , followed by those with H and CH 3 with barriers of 16–17 kcal mol -1 , and then with propargyl radicals with barriers of 24–26 kcal mol -1 . Thus, the OH radical is predicted to be the fastest H abstractor from PAH. Even at 2500 K, the rate constant for H abstraction by H is still 34% lower than the rate constant for H abstraction by OH. The reaction with H is calculated to have rate constants 35–19 times higher than those for the reaction with CH 3 due to a more favorable entropic factor. The reactions of H abstraction by C 3 H 3 are predicted to be orders of magnitude slower than the other reactions considered and their equilibrium is strongly shifted toward the reactants, making propargyl an inefficient H abstractor from the aromatics. The calculations showed strong similarity of the reaction energetics in different H abstraction positions of benzo[a]pyrene and chrysene within armchair and zigzag edges in these molecules, but clear distinction between the armchair and zigzag sites. The zigzag sites appear to be more reactive, with H abstraction rate constants by H, CH 3 , and OH being respectively 37–42%, a factor of 2.1, and factors of 8–9 higher than the corresponding rate constants for the H abstraction reactions from armchair sites. Although the barrier heights for the two types of edges are similar, the entropic factor makes zigzag sites more favorable for H abstraction. Rate expressions have been generated for all studied reactions with the goal to rectify current combustion kinetics mechanisms.

Semenikhin, A. S.↗
DOE OSTI2022

Dissociation-induced depletion of high-energy reactant molecules as a mechanism for pressure-dependent rate constants for bimolecular reactions

In 1922, Lindemann proposed the now-well-known mechanism for pressure-dependent rate constants for unimolecular reactions: reactant molecules with sufficiently high energies dissociate more quickly than collisions can reestablish the Boltzmann distribution of the internal energies of the molecule during its dissociation at low pressures – yielding pressure-dependent rate constants for unimolecular reactions due to the preferential depletion of the high energy states capable of dissociation. In the last century, incredible progress has been made in achieving a far greater understanding of and quantitative predictions for unimolecular and association reactions. In the modern era, pressure-dependent phenomenological rate constants are now nearly universally used to describe the rates of unimolecular and associative reactions in phenomenological kinetic modeling. However, there is a second, more indirect, implication of Lindemann’s mechanism that relates to how these dissociation-induced non-equilibrium distributions impact bimolecular reactions, including non-associative bimolecular reactions – which are generally not considered to have pressure-dependent rate constants. Yet, as we show herein, the same high energy states depleted due to dissociation would otherwise react most rapidly in high-activation-energy bimolecular reactions – yielding a mechanism for pressure-dependent rate constants for bimolecular reactions (including non-associative reactions). Here, we present results from a case study for CH 2 O dissociation, isomerization, and bimolecular reaction with O2 to explore this question. Results from our master equation calculations indicate that the effect of dissociation-induced non-equilibrium distributions on bimolecular reactions can be substantial – even when chemical timescales are well separated from internal energy relaxational timescales (i.e. when the traditional rate constant description would be thought to apply). This effect is found to be more pronounced – and more complex – for bimolecular reactions involving molecular entities whose chemical timescales are merged with the internal energy relaxational timescales. Lastly, we present some ideas for discussion regarding what should be considered as “chemical species” in phenomenological kinetic models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Stability Constants of Lanthanide-nitrate Complexes in Aqueous Solutions: A Theoretical Study

Calculating stability constants for lanthanide--nitrate complexes in aqueous solution is challenging due to the complex free-energy landscapes of the participating species. In this work, we compare cluster-continuum solvation and condensed-phase approaches using universal machine learning interatomic potentials (MLIPs) for determining the stability constants of lanthanide--nitrate complexes in aqueous solutions. Within the cluster--continuum solvation framework at the B3LYP level of theory, reactions involving lanthanide coordination numbers of both 8 and 9 are found to be relevant. After an empirical linear free-energy correction, the cluster--continuum results fall on the same order-of-magnitude scale as the experimental stability constants. By contrast, MACE-MP0 MLIP underestimates lanthanide hydration numbers and gives PMF-derived stability constants with large deviations from experiment, whereas MACE-MATPES-R2SCAN improves both hydration structure and the stability-constant scale but still does not quantitatively reproduce the detailed lanthanide trend. Across both approaches, nitrate binding is best viewed as a labile coordination motif rather than a fixed mono- or bidentate structure, with hydration-shell structure influencing which configurations are favored. Overall, the cluster--continuum calculations provide a practical semi-quantitative baseline for the experimental stability-constant scale, while the explicit-solvent MLIP benchmarks show clear progress from MACE-MP0 to MACE-MATPES-r2SCAN but also highlight the need for lanthanide-targeted training, fine-tuning, or improved long-range and polarization treatments to obtain predictive thermodynamics for complex aqueous lanthanide chemistry.

Dinpajooh, Mohammadhasan↗
NASA NTRS1978

Temperature dependence of the rate constants for reactions of O/1D/ atoms with a number of halocarbons

Results are reported for an experimental study of the reactions of O(1D) with CCl4, CFCl3, CF2Cl2, CHFCl2, CHF2Cl, and CF2ClCFCl2 over the temperature range from 173 to 343 K, based on the time-resolved emission of O(1D) at 630 nm. The experiments involved photolysis of O3 by Nd-YAG laser pulses and measurements of 630-nm emission intensity in mixtures with He and the various halocarbons. Pseudo-first-order rate constants are derived from plots of the logarithms of the 630-nm emission intensities as a function of time for particular He/O3/halocarbon mixtures, and second-order rate constants are then obtained from plots of these pseudo-first-order rate constants as a function of halocarbon concentration at constant He and O3 concentrations. No temperature dependence of the second-order rate constants is observed over the range studied, within the precision of the measurements. It is found that the rate constants decrease as H is substituted for Cl in a halocarbon molecule and as F is substituted for H or Cl.

Davidson, J. A.↗
NASA NTRS1980

Effective optical constants of anisotropic materials

The applicability of a technique for determining the optical constants of soil or aerosol components on the basis of measurements of the reflectance or transmittance of inhomogeneous samples of component material is investigated. Optical constants for a sample of very pure quartzite were obtained by a specular reflection technique and line parameters were calculated by classical dispersion theory. Predictions of the reflectance of powdered quartz were then derived from optical constants measured for the anisotropic quartz and for pure quartz crystals, and compared with experimental measurements. The calculated spectra are found to resemble each other moderately well in shape, however the reflectance level calculated from the psuedo-optical constants (quartzite) is consistently below that calculated from quartz values. The spectrum calculated from the quartz optical constants is also shown to represent the experimental nonrestrahlen features more accurately. It is thus concluded that although optical constants derived from inhomogeneous materials may represent the spectral features of a powdered sample qualitatively a quantitative fit to observed data is not likely.

Aronson, J. R.↗
NASA NTRS1981

The effect of temperature fluctuations of reaction rate constants in turbulent reacting flows

Current models of turbulent reacting flows frequently use Arrhenius reaction rate constants obtained from static or laminar flow theory and/or experiments, or from best fits of static, laminar, and turbulent data. By treating the reaction rate constant as a continuous random variable which is temperature-dependent, the present study assesses the effect of turbulent temperature fluctuations on the reaction rate constant. This model requires that a probability density function (PDF) describing the nature of the fluctuations be specified. Three PDFs are examined: the clipped Gaussian, the beta PDF, and the ramp model. All the models indicate that the reaction rate constant is greater in a turbulent flow field than in an equivalent laminar flow. In addition, an amplification ratio, which is the ratio of the turbulent rate constant to the laminar rate constant, is defined and its behavior as a function of the mean temperature fluctuations is described

Chinitz, W.↗
NASA NTRS1990

Optical constants of solid methane

Methane is the most abundant simple organic molecule in the outer solar system bodies. In addition to being a gaseous constituent of the atmospheres of the Jovian planets and Titan, it is present in the solid form as a constituent of icy surfaces such as those of Triton and Pluto, and as cloud condensate in the atmospheres of Titan, Uranus, and Neptune. It is expected in the liquid form as a constituent of the ocean of Titan. Cometary ices also contain solid methane. The optical constants for both solid and liquid phases of CH4 for a wide temperature range are needed for radiative transfer calculations, for studies of reflection from surfaces, and for modeling of emission in the far infrared and microwave regions. The astronomically important visual to near infrared measurements of solid methane optical constants are conspicuously absent from the literature. Preliminary results are presented on the optical constants of solid methane for the 0.4 to 2.6 micrometer region. Deposition onto a substrate at 10 K produces glassy (semi-amorphous) material. Annealing this material at approximately 33 K for approximately 1 hour results in a crystalline material as seen by sharper, more structured bands and negligible background extinction due to scattering. The constant k is reported for both the amorphous and the crystalline (annealed) states. Typical values (at absorption maxima) are in the .001 to .0001 range. Below lambda = 1.1 micrometers the bands are too weak to be detected by transmission through the films less than or equal to 215 micrometers in thickness, employed in the studies to date. Using previously measured values of the real part of the refractive index, n, of liquid methane at 110 K, n is computed for solid methane using the Lorentz-Lorenz relationship. Work is in progress to extend the measurements of optical constants n and k for liquid and solid to both shorter and longer wavelengths, eventually providing a complete optical constants database for condensed CH4.

Khare, Bishun N.↗
NASA NTRS1996

Experimental and Estimated Rate Constants for the Reactions of Hydroxyl Radicals with Several Halocarbons

Relative rate experiments are used to measure rate constants and temperature dependencies of the reactions of OH with CH3F (41), CH2FCl (31), CH2BrCl (30B1), CH2Br2 (3OB2), CHBr3 (2OB3), CF2BrCHFCl (123aBl(alpha)), and CF2ClCHCl2 (122). Rate constants for additional compounds of these types are estimated using an empirical rate constant estimation method which is based on measured rate constants for a wide range of halocarbons. The experimental data are combined with the estimated and previously reported rate constants to illustrate the effects of F, Cl, and Br substitution on OH rate constants for a series of 19 halomethanes and 25 haloethanes. Application of the estimation technique is further illustrated for some higher hydrofluorocarbons (HFCs), including CHF2CF2CF2CF2H (338pcc), CF3CHFCHFCF2CF3 (43-10mee), CF3CH2CH2CF3 (356ffa), CF3CH2CF2CH2CF3 (458mfcf), CF3CH2CHF2 (245fa), and CF3CH2CF2CH3 (365mfc). The predictions are compared with literature data for these compounds.

DeMore, W.B.↗
NASA NTRS2003

L-band Dielectric Constant Measurements of Seawater (Oral presentation and SMOS Poster)

This paper describes a resonant cavity technique for the measurement of the dielectric constant of seawater as a function of its salinity. Accurate relationships between salinity and dielectric constant (which determines emissivity) are needed for sensor systems such as SMOS and Aquarius that will monitor salinity from space in the near future. The purpose of the new measurements is to establish the dependence of the dielectric constant of seawater on salinity in contemporary units (e.g. psu) and to take advantage of modern instrumentation to increase the accuracy of these measurements. The measurement device is a brass cylindrical cavity 16cm in diameter and 7cm in height. The seawater is introduced into the cavity through a slender glass tube having an inner diameter of 0.1 mm. By assuming that this small amount of seawater slightly perturbs the internal fields in the cavity, perturbation theory can be employed. A simple formula results relating the real part of the dielectric constant to the change in resonant frequency of the cavity. In a similar manner, the imaginary part of the dielectric constant is related to the change in the cavity s Q. The expected accuracy of the cavity technique is better than 1% for the real part and 1 to 2% for the imaginary part. Presently, measurements of methanol have been made and agree with precision measurements in the literature to within 1% in both real and imaginary parts. Measurements have been made of the dielectric constant of seawater samples from Ocean Scientific in the United Kingdom with salinities of 10, 30, 35 and 38 psu. All measurements were made at room temperature. Plans to make measurements at a range of temperatures and salinities will be discussed.

Lang, Roger H.↗
NASA NTRS2004

The Rate Constant for the Reaction H + C2H5 at T = 295 - 150K

The reaction between the hydrogen atom and the ethyl (C2H3) radical is predicted by photochemical modeling to be the most important loss process for C2H5 radicals in the atmospheres of Jupiter and Saturn. This reaction is also one of the major sources for the methyl radicals in these atmospheres. These two simplest hydrocarbon radicals are the initial species for the synthesis of larger hydrocarbons. Previous measurements of the rate constant for the H + C2H5 reaction varied by a factor of five at room temperature, and some studies showed a dependence upon temperature while others showed no such dependence. In addition, the previous studies were at higher temperatures and generally higher pressures than that needed for use in planetary atmospheric models. The rate constant for the reaction H + C2H5 has been measured directly at T = 150, 202 and 295 K and at P = 1.0 Torr He for all temperatures and additionally at P = 0.5 and 2.0 Torr He at T = 202 K. The measurements were performed in a discharge - fast flow system. The decay of the C2H5 radical in the presence of excess hydrogen was monitored by low-energy electron impact mass spectrometry under pseudo-first order conditions. H atoms and C2H5 radicals were generated rapidly and simultaneously by the reaction of fluorine atoms with H2 and C2H6, respectively. The total rate constant was found to be temperature and pressure independent. The measured total rate constant at each temperature are: k(sub 1)(295K) = (1.02+/-0.24)x10(exp -10), k(sub 1)(202K) = (1.02+/-0.22)x10(exp -10) and k(sub 1)(150K) = (0.93+/-0.21)x10(exp -10), all in units of cu cm/molecule/s. The total rate constant derived from all the combined measurements is k(sub 1) = (l.03+/-0.17)x10(exp -10) cu cm/molecule/s. At room temperature our results are about a factor of two higher than the recommended rate constant and a factor of three lower than the most recently published study.

Pimentel, Andre S.↗
NASA NTRS1992

Dielectric constant of liquid alkanes and hydrocarbon mixtures

The complex dielectric constants of n-alkanes with two to seven carbon atoms have been measured. The measurements were conducted using a slotted-line technique at 1.2 GHz and at atmospheric pressure. The temperature was varied from the melting point to the boiling point of the respective alkanes. The real part of the dielectric constant was found to decrease with increasing temperature and correlate with the change in the molar volume. An upper limit to all the loss tangents was established at 0.001. The complex dielectric constants of a few mixtures of liquid alkanes were also measured at room temperature. For a pentane-octane mixture the real part of the dielectric constant could be explained by the Clausius-Mosotti theory. For the mixtures of n-hexane-ethylacetate and n-hexane-acetone the real part of the dielectric constants could be explained by the Onsager theory extended to mixtures. The dielectric constant of the n-hexane-acetone mixture displayed deviations from the Onsager theory at the highest fractions of acetone. The dipole moments of ethylacetate and acetone were determined for dilute mixtures using the Onsager theory and were found to be in agreement with their accepted gas-phase values. The loss tangents of the mixtures exhibited a linear relationship with the volume fraction for low concentrations of the polar liquids.

NASA Program Exobiology↗
NASA NTRS2009

Measurement of the Dielectric Constant of Seawater at L-Band: Techniques and Measurements

Satellite instruments, that will monitor salinity from space in the near future, require an accurate relationship between salinity/temperature and seawater dielectric constant. This paper will review measurements that were made of the dielectric constant of seawater during the past several years. The objective of the measurements is to determine the dependence of the dielectric constant of seawater on salinity and on temperature, more accurately than in the past. by taking advantage of modem instrumentation. The measurements of seawater permittivity have been performed as a function of salinity and temperature using a transmission resonant cavity technique. The measurements have been made in the salinity range of 10 to 38 psu and in the temperature range of IOU C to 35 C. These results will be useful in algorithm development for sensor systems such as SMOS and Aquarius. The measurement system consists of a brass microwave cavity that is resonant at 1.413 GHz. The seawater is introduced into the cavity through a capillary glass tube having an inner diameter of 0.1 mm. The diameter of the tube has been made very small so that the amount of seawater introduced in the cavity is small - thus maintaining the sensitivity of the measurements and allowing the use of perturbation theory predicting the seawater permittivity. The change in resonant frequency and the change in cavity Q can be used to determine the real and imaginary pare of the dielectric constant of seawater introduced into the slender tube. The microwave measurements are made by an HPS722D network analyzer. The cavity has been immersed in a u~ateriethylene-glycol bath which is connected to a Lauda circulator. The circulator keeps the brass cavity at a temperature constant to within 0.01 degrees. The system is automated using a Visual Basic program to control the analyzer and to collect the data. The results of the dielectric constant measurements of seawater will be presented. The measurement results will be compared with permittivity values generated from the Kline and Swift relationship. Two methods of calibration will be discussed, The errors that each technique introduces into the measurement resulls will be reviewed. Temperature stability, frequency drift and the effect of increasing cavity transmission loss on the unloaded cavity Q will also be discussed.

Lang, R.↗
DOE OSTI2019

The Ionization Constants of DCO{sub 3}{sup -} and DPO{sub 4}{sup 2-} under Candu Reactor Primary Coolant Conditions by Raman Spectroscopy

The ionization constants of bicarbonate and hydrogen phosphate have been measured in light and heavy water up to 325 deg. C using Raman spectroscopy. Ionization constants in heavy water at temperatures above 100 deg. C have been measured for very few acids and bases. Together with other results, this work will be used to develop and verify models of the deuterium isotope effect on oxide solubilities in Candu reactor primary coolant. A custom-built titanium/sapphire flow cell was paired with a Horiba Jobin Yvon HR800 LabRAM system to collect Raman spectra of aqueous solutions under Candu primary coolant temperatures. The temperature-controlled cell is made of materials that are relatively inert under the extreme experimental conditions required for hydrothermal studies. Raman spectra were collected with detector polarizations parallel and perpendicular to the laser polarization. These were subtracted and corrected to obtain the reduced isotropic spectrum, which contains only symmetric vibrations, has a flat baseline, and has peak areas proportional to species concentration. Vibrational modes involving deuterium are shifted to lower wavenumbers in heavy water due to the increased mass of deuterium over hydrogen. The speciation between the two solvents is also measurably different. The relative concentration of the acidic species in solution increases with temperature, making its peaks easier to fit at high temperatures. The Raman band positions shift to lower wavenumbers with increasing temperature because the hydrogen bonding in bulk water begins to break down, which strengthens hydrogen bonding to the ions. The basic equilibrium constants were determined from the concentration of each species in solution combined with an activity coefficient model. A simplified form of the 'density' model was then fitted to the data. These fit results were combined with literature values of pK{sub w} in light and heavy water to determine the pK{sub a} values at saturation vapor pressure. The experimental results show excellent agreement with known literature values in light water where they exist at lower temperatures. These equilibrium constants are the first to be reported for both chemical systems in heavy water above 25 deg. C. This work extends the equilibrium constants in H{sub 2}O: - For HCO{sub 3}{sup -} from 250 deg. C to 325 deg. C; - For HPO{sub 4}{sup 2-} from 50 deg. C to 300 deg. C. These are the first ever ionization constants in D{sub 2}O for DPO{sub 4}{sup 2-} and the first values above 25 deg. C for DCO{sub 3}{sup -}. These results will be used to develop predictive models for the deuterium isotope effect on activated corrosion product transport under Candu nuclear reactor primary coolant conditions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

Lifshitz theory of the cosmological constant

Highlights: •Previous attempts to solve the enigma of the cosmological constant have failed. •This paper deduces the correct order of magnitude from the physics of the quantum vacuum. •A dynamical cosmological constant is predicted. •No new fields are introduced, but rather new concepts in fields as old as quantum electromagnetism. -- Abstract: Astrophysics has given empirical evidence for the cosmological constant that accelerates the expansion of the universe. Atomic, Molecular, and Optical Physics have proven experimentally that the quantum vacuum exerts forces – the van der Waals and Casimir forces – on neutral matter. It has long been conjectured (Zel’dovich, 1968) that the two empirical facts, the cosmological constant and the Casimir force, have a common theoretical explanation, but all attempts of deriving both from a unified theory in quantitative detail have not been successful so far. In AMO Physics, Lifshitz theory has been the standard theoretical tool for describing the measured forces of the quantum vacuum. This paper develops a version of Lifshitz theory that also accounts for the electromagnetic contribution to the cosmological constant. Assuming that the other fields of the Standard Model behave similarly, gives a possible quantum-optical explanation for what has been called dark energy.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2018

Quantum Chemical Approach for Calculating Stability Constants of Mercury Complexes

Stability constants are central to the multi-scale modeling of the thermodynamic speciation, cycling, and transport of mercury (Hg) and other contaminants in aquatic environments. However, for Hg, experimental values for many relevant complexes are not available, and for others can span ranges in excess of 10 log units. The missing data and large uncertainties mean there are significant knowledge gaps in predictions of thermodynamic speciation. As an alternative to experimental measurements, thermodynamic quantities can be calculated with quantum chemical methods. Among these, density functional theory (DFT) with a polarizable continuum solvent combines accuracy with practicability. In this paper, we present an accurate and quick approach in which we use DFT with continuum solvation to calculate stability constants of Hg complexes with inorganic and low molecular-weight organic ligands in aqueous solution. Specifically, we use the M06/[SDD]6-31+G(d,p) level of theory in combination with a modified version of the SMD solvent model in which the solute radii are re-optimized with a scaled solvent-accessible surface (sSAS) approach. For the set of 37 Hg complexes used for optimization, which contain environmentally relevant functional groups and have reliable experimental stability constants, we obtain a mean unsigned error of 1.4 log units. Testing the method on an independent set of 12 Hg complexes reproduces the experimental stability constants to a mean unsigned error of 1.6 log units. Finally, this approach is a substantial step toward generally applicable rapid stability constant derivation for a wide range of Hg complexes, including those present in dissolved organic matter.

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

Influence of the Dielectric Constant on the Ionic Current Rectification of Bipolar Nanopores

In this paper, we investigate how the dielectric constant, ϵ, of an electrolyte solvent influences the current rectification characteristics of bipolar nanopores. It is well recognized that bipolar nanopores with two oppositely charged regions rectify current when exposed to an alternating electric potential difference. Here, we consider dilute electrolytes with NaCl only and with a mixture of NaCl and charged nanoparticles. These systems are studied using two levels of description, all-atom explicit water molecular dynamics (MD) simulations and coarse-grained implicit solvent MD simulations. The charge density and electric potential profiles and current-voltage relationship predicted by the implicit solvent simulations with ϵ = 11.3 show good agreement with the predictions from the explicit water simulations. Under nonequilibrium conditions, the predictions of the implicit solvent simulations with a dielectric constant closer to the one of bulk water are significantly different from the predictions obtained with the explicit water model. Further, these findings are closely aligned with experimental data on the dielectric constant of water when confined to nanometric spaces, which suggests that ϵ decreases significantly compared to its value in the bulk. Moreover, the largest electric current rectification is observed in systems containing nanoparticles when ϵ = 78.8. Using enhanced sampling, we have shown that this larger rectification arises from the presence of a significantly deeper minimum in the free energy of the system with a larger ϵ, and when a negative voltage bias is applied. Since implicit solvent models and mean-field continuum theories are often used to design Janus membranes based on bipolar nanopores, this work highlights the importance of properly accounting for the effects of confinement on the dielectric constant of the electrolyte solvent. The results presented here indicate that the dielectric constant in implicit solvent simulations may be used as an adjustable parameter to approximately account for the effects of nanometric confinement on aqueous electrolyte solvents.

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

Optical constants of polycrystalline Al 0.25 Ga 0.75 P and Al 0.9 Ga 0.1 As determined by variable-angle spectroscopic ellipsometry

The optical constants of single-crystal Al x Ga 1-x P and Al x Ga 1-x As have been widely studied at various Al compositions but have not yet been thoroughly investigated as polycrystalline materials. Using variable-angle spectroscopic ellipsometry, we estimate and analyze the optical constants of polycrystalline Al 0.25 Ga 0.75 P and Al 0.9 Ga 0.1 As that were non-epitaxially deposited at deposition temperatures of either 250 or 420 °C, and with various dopant species, dopant concentrations, and V/III flux ratios. Here, for wavelengths of 350–400 nm, decreasing the V/III ratio increases the refractive index of Be-doped polycrystalline Al 0.25 Ga 0.75 P. For wavelengths >500 nm, as the targeted Be dopant concentration increases for polycrystalline Al 0.25 Ga 0.75 P, the amount the extinction coefficient increases and the indirect bandgap decreases depends on the V/III ratio. Furthermore, Si-doped polycrystalline Al 0.25 Ga 0.75 P has significantly smaller extinction coefficient values than when it is Be-doped, for the same V/III ratio and targeted doping concentration, at wavelengths >500 nm. Based on our findings, we hypothesize that the dopant species, dopant concentration, and the V/III ratio dictate various types of defect concentrations, which then affect the optical constants and indirect bandgap of polycrystalline Al 0.25 Ga 0.75 P. Additionally, for wavelengths >500 nm, we find that polycrystalline Al 0.25 Ga 0.75 P and Al 0.9 Ga 0.1 As have the lowest extinction coefficient values when deposited at 420 °C, as opposed to 250 °C. Thus, we hypothesize that the deposition temperature is the most significant factor in dictating the optical constants of these polycrystalline III-Vs. Ultimately, this work demonstrates alternative methods to tune the optical constants of polycrystalline Al 0.25 Ga 0.75 P and Al 0.9 Ga 0.1 As, as opposed to tuning the Al composition.

42 ENGINEERING↗