High Concentration Regime Research Articles

Transitioning from Regular Electrolytes to Solvate Ionic Liquids to High-Concentration Electrolytes: Changes in Transport Properties and Ionic Speciation.

Glyme-based lithium-ion electrolytes have received considerable attention from the scientific community due to their improved safety, as well as electrochemical and thermal stability over carbonate-based electrolytes. However, these electrolytes suffer from major drawbacks such as high viscosities. To overcome the challenges that hinder their full potential, the molecular description of glyme-based lithium electrolytes in the high-concentration regime, particularly in the solvate ionic liquid (SIL) and high-concentration electrolyte (HCE) regimes, is needed. In this study, model glyme-based electrolytes based on a lithium thiocyanate and either tetraglyme (G4) or a mixture of monoglyme (G1) and diglyme (G2) were investigated as a function of the solvent-to-lithium ratio using linear and nonlinear IR spectroscopies, in combination with ab initio computations as well as electrochemical methods . The transport properties reveal enhanced ionicities in the HCE and SIL regimes ([O]/[Li] ≤ 5) compared to the regular electrolytes (REs, with [O]/[Li] > 5) in both pure (G4) and mixed (G1:G2) glymes. IR and ab initio computations relate these larger ionicities to the higher concentration of charged aggregates in the HCE and SIL electrolytes ([O]/[Li] ≤ 5). Moreover, it was observed that the use of mixed glymes appears to have a minimal effect on the transport properties of REs but exhibits deleterious effects on SILs. Overall, the results provide a molecular framework for describing the local structure of lithium glyme-based electrolytes and demonstrate the key role that the nature of glyme solvation plays in the molecular structure and consequently the macroscopic properties of the Li-glyme SILs, HCEs, and REs.

Achieving High Substitutional Incorporation in Mn-Doped Graphene.

Despite its broad potential applications, substitution of carbon by transition metal atoms in graphene has so far been explored only to a limited extent. We report the realization of substitutional Mn doping of graphene to a record high atomic concentration of 0.5%, which was achieved using ultralow-energy ion implantation. By correlating the experimental data with the results of ab initio Born-Oppenheimer molecular dynamics calculations, we infer that direct substitution is the dominant mechanism of impurity incorporation. Thermal annealing in ultrahigh vacuum provides efficient removal of surface contaminants and additional implantation-induced disorder, resulting in Mn-doped graphene that, aside from the substitutional Mn impurities, is essentially as clean and defect-free as the as-grown layer. We further show that the Dirac character of graphene is preserved upon substitutional Mn doping, even in this high concentration regime, making this system ideal for studying the interaction between Dirac conduction electrons and localized magnetic moments. More generally, these results show that ultralow energy ion implantation can be used for controlled functionalization of graphene with substitutional transition-metal atoms, of relevance for a wide range of applications, from magnetism and spintronics to single-atom catalysis.

Analysing Spatiotemporal Variability of Chlorophyll-a Concentration and Water Surface Temperature in Coastal Lagoons of the Ebro Delta (NW Mediterranean Sea, Spain)

Coastal lagoons are highly productive transitional water bodies threatened by human factors and vulnerable to global climate change effects. Monitoring biophysical parameters in these ecosystems is crucial for their preservation. In this work, we used Sentinel-2 and Landsat imagery combined with in situ data to (1) develop preliminary algorithms for retrieving the Chl-a concentration and water surface temperature of six lagoons located in the Ebro Delta (NE Mediterranean Sea, Spain), and to (2) compute maps and trend lines for analysing their spatiotemporal evolution from 2015 to 2022. Our findings showed that the algorithms’ accuracy ranged from 72% to 78% and had limited potential under high Chl-a concentration regimes. Even so, they revealed the lagoons’ trophic status, usual fluctuations, and deviations of both parameters attributed to seasonal (i.e., light and temperature) and short-term physical (i.e., winds) forcing, as well as valuable spatial patterns potentially useful for conservation efforts and land use planning. Future work will focus on the acquisition of a larger in situ data sample under a range of environmental conditions to improve the algorithms’ robustness, which in turn will allow the investigation of natural and human factors controlling the dynamics of the two investigated parameters.

Effect of impurities and carrier concentration on conductivity of bilayer graphene double layer system in different dielectric environments

The electronic transport properties of the bilayer graphene double layer (BLGDL) system at [Formula: see text][Formula: see text]K using the Boltzmann transport equation are reported here. The conductivity of the BLGDL system has been calculated with varying parameters as relative carrier concentration [Formula: see text], short-range (point defect) and long-range (Coulomb charge) impurity concentration, relative dielectric constant [Formula: see text] and interlayer distance [Formula: see text]. The maximum conductivity has been achieved in the absence of short-range impurity. The short-range impurity plays a non-trivial meaningful role in high dielectric and high carrier concentration regimes and limits the conductivity. For higher [Formula: see text] and higher [Formula: see text] values, the nature of the conductivity curve turns out to be of a sublinear nature, while in all other cases, it shows a superlinear trend. Suitable selection of relative dielectric constants, relative carrier concentration and interlayer distance helps to improve the conductivity of the BLGDL system. If the dielectric constant of the spacer is higher than the substrate material, the thickness of the spacer material helps remarkably in enhancing conductivity. Moreover, a comparison of BLGDL with our previously reported MLG–MLG double layer graphene system (DLGS) confirms that higher conductivity is achieved in the case of BLG–BLG system compared to DLGS.

NaCl, MgCl2, and AlCl3 Surface Coverages on Fused Silica and Adsorption Free Energies at pH 4 from Nonlinear Optics.

We employ amplitude- and phase-resolved second harmonic generation experiments to probe interactions of fused silica:aqueous interfaces with Al3+, Mg2+, and Na+ cations at pH 4 and as a function of metal cation concentration. We quantify the second-order nonlinear susceptibility and the total interfacial potential in the presence and absence of a 10 mM screening electrolyte to understand the influence of charge screening on cation adsorption. Strong cation:surface interactions are observed in the absence of the screening electrolyte. The total potential is then employed to estimate the total number of absorbed cations cm-2. The contributions to the total potential from the bound and mobile charges were separated using Gouy-Chapman-Stern model estimates. All three cations bind fully reversibly, indicating physisorption as the mode of interaction. Of the isotherm models tested, the Kd adsorption model fits the data with binding constants of 3-30 and ∼300 mol-1 for the low (<0.1 mM) and high (0.1-3 mM) concentration regimes, corresponding to adsorption free energies of -13 to -18 and -24 kJ mol-1 at room temperature, respectively. The maximum surface coverages are around 1013 cations cm-2, matching the number of deprotonated silanol groups on silica at pH 4. Clear signs of decoupled Stern and diffuse layer nonlinear optical responses are observed and found to be cation-specific.

A multi-scale numerical approach to study monoclonal antibodies in solution.

Developing efficient and robust computational models is essential to improve our understanding of protein solution behavior. This becomes particularly important to tackle the high-concentration regime. In this context, the main challenge is to put forward coarse-grained descriptions able to reduce the level of detail, while retaining key features and relevant information. In this work, we develop an efficient strategy that can be used to investigate and gain insight into monoclonal antibody solutions under different conditions. We use a multi-scale numerical approach, which connects information obtained at all-atom and amino-acid levels to bead models. The latter has the advantage of reproducing the properties of interest while being computationally much faster. Indeed, these models allow us to perform many-protein simulations with a large number of molecules. We can, thus, explore conditions not easily accessible with more detailed descriptions, perform effective comparisons with experimental data up to very high protein concentrations, and efficiently investigate protein-protein interactions and their role in phase behavior and protein self-assembly. Here, a particular emphasis is given to the effects of charges at different ionic strengths.

Visible-Light Driven Control Over Triply and Quadruply Hydrogen-Bonded Supramolecular Assemblies.

Supramolecular polymers offer tremendous potential to produce new "smart" materials, however, there remains a need to develop systems that are responsive to external stimuli. In this work, visible-light responsive hydrogen-bonded supramolecular polymers comprising photoresponsive supramolecular synthons (I-III) consisting of two hydrogen bonding motifs (HBMs) connected by a central ortho-tetrafluorinated azobenzene have been characterized by DOSY NMR and viscometry. Comparison of different hydrogen-bonding motifs reveals that assembly in the low and high concentration regimes is strongly influenced by the strength of association between the HBMs. I, Incorporating a triply hydrogen-bonded heterodimer, was found to exhibit concentration dependent switching between a monomeric pseudo-cycle and supramolecular oligomer through intermolecular hydrogen bonding interactions between the HBMs. II, Based on the same photoresponsive scaffold, and incorporating a quadruply hydrogen-bonded homodimer was found to form a supramolecular polymer which was dependent upon the ring-chain equilibrium and thus dependent upon both concentration and photochemical stimulus. Finally, III, incorporating a quadruply hydrogen-bonded heterodimer represents the first photoswitchable AB type hydrogen-bonded supramolecular polymer. Depending on the concentration and photostationary state, four different assemblies dominate for both monomers II and III, demonstrating the ability to control supramolecular assembly and physical properties triggered by light.

A Unified Description of Salt Effects on the Liquid-Liquid Phase Separation of Proteins.

Protein aggregation via liquid-liquid phase separation (LLPS) is ubiquitous in nature and is intimately connected to many human diseases. Although it is widely known that the addition of salt has crucial impacts on the LLPS of proteins, full understanding of the salt effects remains an outstanding challenge. Here, we develop a molecular theory that systematically incorporates the self-consistent field theory for charged macromolecules into the solution thermodynamics. The electrostatic interaction, hydrophobicity, ion solvation, and translational entropy are included in a unified framework. Our theory fully captures the long-standing puzzles of the nonmonotonic salt concentration dependence and the specific ion effect. We find that proteins show salting-out at low salt concentrations due to ionic screening. The solubility follows the inverse Hofmeister series. In the high salt concentration regime, protein continues salting-out for small ions but turns to salting-in for larger ions, accompanied by the reversal of the Hofmeister series. We reveal that the solubility at high salt concentrations is determined by the competition between the solvation energy and translational entropy of the ion. Furthermore, we derive an analytical criterion for determining the boundary between the salting-in and salting-out regimes, which is in good agreement with experimental results for various proteins and salt ions.

Reexpansion of charged nanoparticle assemblies in concentrated electrolytes

Electrostatic forces in solutions are highly relevant to a variety of fields, ranging from electrochemical energy storage to biology. However, their manifestation in concentrated electrolytes is not fully understood, as exemplified by counterintuitive observations of colloidal stability and long-ranged repulsions in molten salts. Highly charged biomolecules, such as DNA, respond sensitively to ions in dilute solutions. Here, we use non-base-pairing DNA-coated nanoparticles (DNA-NP) to analyze electrostatic interactions in concentrated salt solutions. Despite their negative charge, these conjugates form colloidal crystals in solutions of sufficient divalent cation concentration. We utilize small-angle X-ray scattering (SAXS) to study such DNA-NP assemblies across the full accessible concentration ranges of aqueous CaCl2, MgCl2, and SrCl2 solutions. SAXS shows that the crystallinity and phases of the assembled structures vary with cation type. For all tested salts, the aggregates contract with added ions at low salinities and then begin expanding above a cation-dependent threshold salt concentration. Wide-angle X-ray scattering (WAXS) reveals enhanced positional correlations between ions in the solution at high salt concentrations. Complementary molecular dynamics simulations show that these ion-ion interactions reduce the favorability of dense ion configurations within the DNA brushes below that of the bulk solution. Measurements in solutions with lowered permittivity demonstrate a simultaneous increase in ion coupling and decrease in the concentration at which aggregate expansion begins, thus confirming the connection between these phenomena. Our work demonstrates that interactions between charged objects continue to evolve considerably into the high-concentration regime, where classical theories project electrostatics to be of negligible consequence.

Organic-Inorganic hybrid membrane for simultaneous heavy metal removal at drinking water pollution concentration levels

This study proposes a novel approach for simultaneous removal of potentially toxic metals from contaminated drinking water. The strategy is based on multi-layer graphene oxide hybrid membranes made up of Fe3O4@amyloid fibrils nanoclusters intercalated into the graphene oxide sheets via flow through approach. The hybrid membrane outperforms the previously known graphene-based membranes with adsorption capacity in the range of 128–570 mg g−1 of material. The membrane's removal efficacy exceeds 99.9% in both low (150 µg/L) and high (10,000 µg/L) metal concentration regimes, representative of ground water and wastewater contamination and complies with WHO drinking water requirements. Following NSF/ANSI 42,53–2007a American Standard Regulations, samples with metal concentrations of 150 µg/L and 20 mg L−1 calcium coexisted at pH 6.5 ± 0.25, complete removal of heavy metals (100%) in the effluent was observed. Benchmark testing on real municipal and ground water samples in continuous operation mode shows that ∼ 7500 and 5000 L water/g of membrane were treated well while maintaining WHO drinking water standards. The saturated membrane regenerated and successfully reused several times without losing purification performance. The present technique shows a great deal for addressing the worldwide problem of contaminated drinking water due to good selectivity, low fabrication cost, and excellent performance on real water.

Far-Field Polarization Optics Control the Nanometer-Scale Pattern of High-Fluorescence Dissymmetry Emission from Achiral Molecules near Plasmonic Nanodimers

Chiroptical spectroscopies like circular dichroism report on the handedness of molecules but are often limited to the high-concentration regime because of the mismatch between the wavelength of propagating visible light and the size of molecules. Recent work has demonstrated that the electromagnetic fields generated near chiral plasmonic nanostructures can have high optical chirality that bridges these length scales and can induce high-fluorescence dissymmetry signals from achiral dyes by redirecting their emission. As a step toward single-molecule chiral sources, the induced fluorescence dissymmetry and apparent emission pattern near chiral plasmonic nanoparticles must be quantified. Here, we measure the induced fluorescence dissymmetry from the achiral dye Cy5.5 near a chiral gold nanodimer structure, and we map out the apparent emission pattern of the dyes using super-resolution single-molecule microscopy. Our high-sensitivity approach quantifies the fluorescence dissymmetry from sampling only ∼100 zeptomoles of Cy5.5 and measures from Cy5.5 near gold nanodimers median fluorescence dissymmetry factors that are 2 orders of magnitude greater than those of synthesized chiral fluorescent molecules. We observe a spatial correlation between the simulated optical chirality about a plasmonic gold nanodimer and experimentally obtained super-resolution apparent emission patterns, and we use the incident polarization to control our detection bias for the brightest molecules to sample nanometer-scale regions of high electric flux.

Hot Isostatic Pressing Control of Tungsten-Based Composites

Metal-oxide composites are commonly used in high temperature environments for their thermal stability and high melting points. Commonly employed with refractory oxides or carbides such as ZrC and HfC, these materials may be improved with the use of a low density, high melting point ceramic such as CeO2. In this work, the consolidation of W-CeO2 metal matrix composites in the high CeO2 concentration regime is explored. The CeO2 concentrations of 50, 33, and 25 wt.%, the CeO2 particle size from nanometer to micrometer, and various hot isostatic pressing temperatures are investigated. Decreasing the CeO2 concentration is observed to increase the composite density and increase the Vickers hardness. The CeO2 oxidation state is observed to be a combination of Ce3+ and Ce4+, which is hypothesized to contribute to the porosity of the composites. The hardness of the metal-oxide composite can be improved more than 2.5 times compared to pure W processed by the same route. This work offers processing guidelines for further consolation of oxide-doped W composites.

Real-time monitoring of toxic CS2 with high concentrations using a suitable terahertz photonic crystal fiber

Detection of toxic carbon disulfide ( C S 2 ) at high concentration, arising due to heavy industrial utilities, is an essential requirement for a sustainable ecosystem and healthcare. However, research and development of appropriate sensor devices to monitor a very high concentration of C S 2 are lacking. We design a polyethylene (PE) photonic crystal fiber (PCF) consisting of two interpenetrating periodic hexagonal lattices of teflon inclusions and air holes in the cladding, which can monitor ambient C S 2 with extremely high precision in a wide concentration range. Here, we measure the time delay difference (TDD) associated with the difference between group velocities of the two supported modes due to changes in C S 2 concentration in the prescribed holes. For a 10 cm long variant of the designed PCF operating at 0.75 THz frequency, we observe a linearly increasing TDD variation from ∼ 2 to 13 ps due to change in C S 2 concentration from 17 to 50%. However, when the C S 2 concentration exceeds the 50% range, we observe decreasing TDD characteristics. In this high concentration regime ( &gt; --> 50 % ), we monitor C S 2 by analyzing second mode loss (SML) variation due to concentration change (at 0.98 THz frequency), where SML increases up to ∼ 30 d B for ∼ 100 % ambient C S 2 concentration. Here, we achieve a high concentration sensitivity where a variation of 1.6 dB SML is observed with a unit concentration change of C S 2 . The proposed scheme has an immense potential to boost the technologies for high-precision gas monitoring devices.

How do cell crowding and starvation affect avascular tumor growth of the EMT6/Ro tumor?

Here we re-examine experimental in vitro data for the EMT6/Ro tumor volume and viable rim thickness. This shows that the growth speed is constant in time, and independent of nutrient concentration at large concentrations, but that the viable rim thickness increases in this high concentration regime. We then present a simple mechanistic reaction-diffusion equation that includes crowding and starvation effects, and show that the model qualitatively captures the experimental observations. Moreover, the model predicts that the cancer cell concentration is characterised by a wave pulse (soliton), and the pulse shape is explored through zero’th order perturbation analysis corresponding to large wave speeds. It is shown that this zero’th order term is dominant for the experimental condition, further indicating that the non-linear reaction governs the pulse characteristic shape. Finally, at low nutrient concentrations we find that the front is a pulled-front, that is, the growth speed is determined by the cell multiplication at the wave front edge in accordance with earlier modelling approaches.

Unexpected Slow Kinetics of Poly(Methacrylic Acid) Phase Separation in the Semi-Dilute Regime.

Poly (methacrylic acid) (PMAA) solutions are known to exhibit a lower critical solution temperature (LCST). A temperature-composition phase diagram of PMAA has been constructed by standard cloud point determination through transmittance measurements, and also by studying the steady states reached under phase separation. This allows us to reconstruct the binodal curve describing the phase behavior of PMAA for both low and high concentration regimes, and to determine accurately the LCST temperature. In a second step, the structures formed following a temperature jump above the cloud point and their evolution in time have been investigated at the nanoscale using small angle neutron scattering (SANS). This approach shows that the formation of phase-separated nanostructures is a slow process, requiring more than 12 h. The formed structures are then shown to depend on the amplitude of the temperature jump above the cloud point. An original mechanism of phase separation is identified in the semi-dilute regime. The growth of micrometric-size droplets with an inner structure displaying the rheological properties of a gel leads to the formation of a percolating network which hinders the influence of gravity. Such a result can explain the slow kinetics of the PMAA LCST transition.

Ion Transport and Electrochemical Stability of Polyacrylonitrile (PAN) Based Electrolytes

Polyacrylonitrile (PAN) is one of the alternative candidate polymer hosts to form solid polymer electrolytes (SPEs) besides the widely used poly(ethylene oxide). However, over 3 orders of magnitude of discrepancy in ionic conductivity has been reported in PAN-based SPEs, in both the low salt concentration and the high salt concentration regimes. This discrepancy originates from different film processing conditions. In this study, we rigorously examine how processing conditions, including solution mixing, casting, and drying conditions affect the morphology, ion transport, solvation structure, Li and oxidative stability of PAN based electrolytes. It is found that the ion transport, lithium stability and the oxidative stability of PAN-based SPEs are critically dependent on the residual dimethylformamide (DMF) solvent content. We systematically study four different drying conditions and the resulting residual solvent is quantified by infrared spectroscopy. We demonstrate that conductivity variation across 5 orders of magnitude can be obtained depending on the drying conditions. Furthermore, the effects of residual DMF solvent on the ion transport mechanism, stability against lithium and the oxidative stability are elucidated. This thorough study lays the groundwork for future development of PAN based electrolytes.

Formation and development of distinct deposit patterns by drying Polyelectrolyte-stabilized colloidal droplets at different surfactant concentrations

Understanding and controlling the formation of various deposit patterns such as coffee stains, multiple ring-like morphologies, and uniform deposition are essential for developing various applications. The presence of polymer and surfactant in a drying colloidal droplet can alter the droplet evaporation mode and deposit structure. In this work, we study the effect of Marangoni stresses on the evaporative dynamics and the structure and alignment of nanoparticles in the dried deposit patterns when a droplet of electro-sterically stabilized (poly(styrene sulfonate)) gold nanorod dispersion (PSS Au-NR) dries on a hydrophilic silicon substrate at low and high concentration regimes of an added surfactant (CTAB). The evaporative kinetics study shows that the evaporating droplets of PSS Au-NR dispersion exhibit rapid pinning and quick evaporation at zero and high CTAB concentrations, which transforms to three stages of droplet evaporation with an initial droplet depinning stage at low CTAB concentration. Pinning of the PSS Au-NR dispersion droplet in the absence of CTAB results in a coffee stain with densely and loosely packed PSS Au-NRs without any nanorod ordering in the outer and inner coffee stain edges. The formation and systematic evolution of various new deposit structures such as depinned region, depletion region, and fingering pattern are noted both outside and inside the coffee stain at different CTAB concentrations. Our study demonstrates that the kinetics of droplet drying and the deposit pattern of an evaporating polyelectrolyte-colloidal droplet can be tailored systematically by controlling the internal flows in the droplet dispersion medium through the addition of surfactant.

Salt-Induced Transitions in the Conformational Ensembles of Intrinsically Disordered Proteins.

Salts modulate the behavior of intrinsically disordered proteins (IDPs) and influence the formation of membraneless organelles through liquid-liquid phase separation (LLPS). In low ionic strength solutions, IDP conformations are perturbed by the screening of electrostatic interactions, independent of the salt identity. In this regime, insight into the IDP behavior can be obtained using the theory for salt-induced transitions in charged polymers. However, salt-specific interactions with the charged and uncharged residues, known as the Hofmeister effect, influence IDP behavior in high ionic strength solutions. There is a lack of reliable theoretical models in high salt concentration regimes to predict the salt effect on IDPs. We propose a simulation methodology using a coarse-grained IDP model and experimentally measured water to salt solution transfer free energies of various chemical groups that allowed us to study the salt-specific transitions induced in the IDPs conformational ensemble. We probed the effect of three different monovalent salts on five IDPs belonging to various polymer classes based on charged residue content. We demonstrate that all of the IDPs of different polymer classes behave as self-avoiding walks (SAWs) at physiological salt concentration. In high salt concentrations, the transitions observed in the IDP conformational ensembles are dependent on the salt used and the IDP sequence and composition. Changing the anion with the cation fixed can result in the IDP transition from a SAW-like behavior to a collapsed globule. An important implication of these results is that a suitable salt can be identified to induce condensation of an IDP through LLPS.

Exacerbation of PM2.5 concentration due to unpredictable weak Asian dust storm: A case study of an extraordinarily long-lasting spring haze episode in Seoul, Korea

Severe haze episodes have occurred frequently throughout megacities in East Asia, especially during winter and early spring. Although notable progress has been attained in understanding the causes of severe haze formation, the exacerbation of PM2.5 concentration due to Asian dust has not yet been fully investigated. Here, we investigated the contribution of weak Asian dust particles to PM2.5 concentration during early spring for an extraordinarily long-lasting high PM2.5 episode in Seoul, Korea. PM2.5 concentrations exceeding national criteria (35 μg m−3) were continuously observed from February 27 to March 7, 2019, and can be attributable to the transboundary transported aerosols for the Asian continent under slow eastward-migrating anticyclones. The high-frequency of PM10-2.5 and PM2.5 mass concentrations in the high concentration regime (PM10-2.5 > 30 μg m−3; PM2.5 > 80 μg m−3) suggests that Asian dust particles transported concurrently with anthropogenic pollution aerosols contributed to elevated PM2.5 concentration during this episode. This was also evident from an elevated depolarization ratio (δ532: 0.06–0.13) and aerosol volume concentrations both in coarse and fine modes, which indicates the presence of non-spherical dust particles, from collocated aerosol lidar and optical particle counter measurements. Unlike severe Asian dust episodes (PM10 > 800 μg m−3) in Korea, relatively low Asian dust particle concentrations during high PM2.5 haze episodes have not been accurately predicted and alerted by most air quality forecasting models. This study emphasizes the need for the implementation of a series of dust emission and transport processes for better predictions of PM2.5 concentration during winter-spring high PM2.5 episodes.

Effects of dynamic disorder on thermoelectric transport in soft materials

A model is developed that accounts for the effects of thermal disorder (both static and dynamic) in predicting the thermoelectric (TE) performance of weakly bonded semiconductors. With dynamic disorder included, the model is found to fit well with experimental results found in the literature for the density-of-states and the energy-dependent carrier mobility, which are key for assessing TE properties. The model is then used to analyze the concentration-dependent TE properties of the prototypical small molecular semiconductor rubrene. At low (e.g., intrinsic) carrier concentrations, where Fermi level pinning occurs, dynamic disorder is found to reduce electrical conductivity (σ), Seebeck coefficient (S), and thermoelectric power factor (PF) to values that are much lower than those traditionally predicted by static disorder models. As carrier concentration (p) increases, S exhibits nonlinear behavior, increasing well above the conventional S vs log(p) relationship before reaching a peak value (Speak∼1550μV/K). A critical carrier concentration (pcrit.≈4.299×10−4 molar ratio) is observed near Speak at which thermoelectric transport transitions from trap-limited behavior at low concentrations to conventional band behavior at high concentrations. Above this value, σ and PF are reduced compared to the perfect crystal and static-only conditions, causing a drop in the maximum PF by factors of 3 and 2.3, respectively. This PF reduction, while not as large as the PF reduction that occurs for low carrier concentration, is found to occur in a high concentration regime (p&amp;gt;pcrit.) that contains the PF maximum and has remained inaccessible to experimentalists due to dopant limitations that are worsened in the presence of dynamic disorder.