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DOE OSTI2026

Dramatic Slowdown of Bimolecular Reactions of Criegee Intermediates in Organic Aerosols

Although Criegee intermediates (CIs) play a central role in driving the transformation of organic molecules, their condensed-phase reaction kinetics remains poorly understood. While CIs undergo unimolecular decomposition to produce OH radicals, stabilized CIs participate in a host of other bimolecular reactions forming larger molecular weight products, including secondary ozonides (kSOZ), alkoxyalkyl hydroperoxides (kAlAHP), and acyloxyalkyl hydroperoxides (kAcAHP). Here, we demonstrate, using prior literature and new measurements of heterogeneous organic aerosol reactions using O3 or OH radicals, that these condensed-phase bimolecular reaction rate coefficients kSOZ (10-20 cm3·molecule-1·s-1), kAlAHP, and kAcAHP (10-19 cm3·molecule-1·s-1) are 7-10 orders of magnitude slower than analogous gas-phase reactions (∼ 10-10-10-13 cm3·molecule-1·s-1). This contrasts with current evidence that the rate coefficients for unimolecular steps in the condensed phase are similar in magnitude to those in the gas phase. Kinetic models using gas-phase-like bimolecular coefficients consistently overestimate the importance of bimolecular relative to unimolecular pathways while underpredicting the aerosol reactivity by up to 30-fold. The slowing of bimolecular reactivity in aerosols is likely due to solvation effects and the increased steric hindrance of larger molecular weight CIs and their scavengers in the condensed phase. These results challenge the conventional view that the high reactant density of an organic aerosol should favor bimolecular over unimolecular reactions, underscoring the need for more accurate CI condensed-phase rate constants for reliable modeling of oxidative processes across a diverse set of atmospheric and environmental systems.

Zeng, Meirong↗

DOE OSTI2019

Utilizing Charge Effects and Minimizing Intramolecular Proton Rearrangement to Improve the Overpotential of a Thiosemicarbazonato Zinc HER Catalyst

The zinc(II) complex of diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-hydrazonepyridine), ZnL 1 (1), was prepared and evaluated as a precatalyst for the hydrogen evolution reaction (HER) under homogeneous conditions in acetonitrile. Complex 1 is protonated on the noncoordinating nitrogen of the hydrazonepyridine moiety to yield the active catalyst Zn(HL 1 )OAc (2) upon addition of acetic acid. Addition of methyl iodide to 1 yields the corresponding methylated derivative ZnL 2 I (3). In solution, partial dissociation of the coordinated iodide yields the cationic derivative 3'. Complexes 1–3 were characterized by 1 H NMR, FT-IR, and UV–visible spectroscopies. The solid-state structures of 2 and 3 were determined by single crystal X-ray diffraction. HER studies conducted in acetonitrile with acetic acid as the proton source yield a turnover frequency (TOF) of 7700 s –1 for solutions of 1 at an overpotential of 1.27 V and a TOF of 6700 s –1 for solutions of 3 at an overpotential of 0.56 V. For both complexes, the required potential for catalysis, E cat/2 , is larger than the thermodynamic reduction potential, E 1/2 , indicative of a kinetic barrier attributed to intramolecular proton rearrangement. The effect is larger for solutions of 1 (+440 mV) than for solutions of 3 (+160 mV). Controlled potential coulometry studies were used to determine faradaic efficiencies of 71 and 89% for solutions of 1 and 3, respectively. For both catalysts, extensive cycling of potential under catalytic conditions results in the deposition of a film on the glassy carbon electrode surface that is active as an HER catalyst. Analysis of the film of 3 by X-ray photoelectron spectroscopy indicates the complex remains intact upon deposition. A proposed ligand-centered HER mechanism with 1 as a precatalyst to 2 is supported computationally using density functional theory (DFT). All catalytic intermediates in the mechanism were structurally and energetically characterized with the DFT/B3LYP/6-311g(d,p) in solution phase using a polarizable continuum model (PCM). Finally, the thermodynamic feasibility of the mechanism is supported by calculation of equilibrium constants or reduction potentials for each proposed step.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Hydrogenation of ethylene over molybdenum–sulfur complexes supported on UiO-66

Development of supported single-site catalysts using small metal sulfide complexes could significantly help in the development of cost-effective catalytic materials to drive selective hydrogenation and hydrogenolysis. The goal of this study is to contribute to the development of metal sulfide catalysts by calculating the thermodynamics of a catalytic cyclic involving a metal organic framework functionalized by insertion of metal sulfide. Anchored metal sulfide complexes can potentially be designed with ligands with distinctly different electronic and catalytic properties for specific catalytic applications. Here we examine the hydrogenation of ethylene as a model. We use density functional theory to investigate molybdenum–sulfur complexes as active catalysts anchored on the metal–organic framework UiO-66 as a stable support. Our calculations show that the anchored complexes with more than two sulfur ligands are unfavorable for ethylene adsorption, so we study complexes with one or two sulfur ligands. Hydrogenation of the unsaturated carbon double bond requires the transfer of two hydrogen atoms, which can occur via heterolytic activation of hydrogen to form a Mo-hydride and a protonated sulfur – either by hydride transfer followed by proton transfer or via proton transfer followed by hydride transfer, and we find that both mechanisms proceed via two-state reactivity involving two spin states along the reaction path. Of the two catalysts studied in gas the phase, the MoS single-sulfur–ligand complex with lower oxidation states produces thermodynamically more favorable intermediates along the pathway for the first hydrogen transfer for both the hydride-first mechanism and the proton-first mechanism. As a result, the quantum mechanical calculations provide experimentally inaccessible partial atomic charges and geometries of the various intermediates encountered along the steps of the reaction mechanisms.

Kermani, Maryam Mansoori [University of Minnesota,↗

DOE OSTI2021

Influence of elongation and triangularity on plasma response to resonant magnetic perturbations

Abstract Systematic toroidal modeling of the plasma response to the n = 1–4 ( n is the toroidal mode number) resonant magnetic perturbation (RMP) field is carried out in order to understand the plasma-shaping effect on controlling the type-I edge-localized modes (ELMs) in tokamak experiments. Considered are large variations of the plasma elongation and triangularity at a fixed edge safety factor q a , for limiter plasmas with both single-null (SN) and double-null (DN) divertor-like boundary shapes. Numerical results assuming conformal 3D RMP coils show that (i) the optimum coil phasing between the upper and lower rows for ELM control becomes increasingly sensitive to the plasma elongation with higher- n toroidal spectra, (ii) the optimum coil phasing is however essentially independent of the plasma triangularity for all n = 1–4 RMP fields, (iii) with the same coil current and the optimum coil phasing, high elongation generally favors ELM control but it may be more challenging for plasmas with intermediate elongation and with lower- n ( n = 1–2) RMPs, and (iv) higher triangularity is generally always better for ELM control with all n = 1–4 fields for both DN and SN divertor-like plasma boundary shapes.

Physics↗

DOE OSTI2017

Effect of Sr doping on the magnetic exchange interactions in manganites of type L a 1 - x S r x M n y A 1 - y O 3 ( A = Ga , Ti ; 0.1 ≤ y ≤ 1 )

Strontium doping transforms manganites of type La 1 - x Sr x Mn O 3 from an insulating antiferromagnet ( x = 0 ) to a metallic ferromagnet ( x > 0.16 ) due to the induced charge carriers (holes). We employed neutron scattering experiments in order to investigate the effect of Sr doping on a tailor-made compound of composition La 0.7 S r 0.3 M n 0.1 Ti 0.3 G a 0.6 O 3 . By the simultaneous doping with S r 2 + and Ti 4 + ions, the compound remains in the insulating state so that the magnetic interactions for large Sr doping can be studied in the absence of charge carriers. At T C = 215 K , there is a first-order reconstructive phase transition from the trigonal R - 3 c structure to the orthorhombic Pnma structure via an intermediate virtual configuration described by the common monoclinic subgroup P2 1 / c . The magnetic excitations associated with Mn 3 + dimers give evidence for two different nearest-neighbor ferromagnetic exchange interactions, in contrast to the undoped compound LaM n y A 1 - y O 3 where both ferromagnetic and antiferromagnetic interactions are present. Furthemore, the doping-induced changes of the exchange coupling originates from different Mn-O-Mn bond angles determined by neutron diffraction. The large fourth-nearest-neighbor interaction found for metallic manganites is absent in the insulating state. Here, we argue that the Ruderman-Kittel-Kasuya-Yosida interaction reasonably accounts for all the exchange couplings derived from the spin-wave dispersion in metallic manganites.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2011

Unifying Interfacial Self-Assembly and Surface Freezing

X-ray investigations reveal that the monolayers formed at the bulk alkanol-sapphire interface are densely packed with the surface-normal molecules hydrogen bound to the sapphire. About 30-35 C above the bulk, these monolayers both melt reversibly and partially desorb. This system exhibits balanced intermolecular and molecule-substrate interactions which are intermediate between self-assembled and surface-frozen monolayers, each dominated by one interaction. The phase behavior is rationalized within a thermodynamic model comprising interfacial interactions, elasticity, and entropic effects. Separating the substrate from the melt leaves the monolayer structurally intact.

08 HYDROGEN↗

DOE OSTI2014

SU-E-T-620: Dosimetric Compliance Study for a New Prostate Protocol of Combined High Dose Rate Brachytherapy and Stereotactic Body Radiotherapy

Purpose: To investigate the adherence of treatment plans of prostate cancer patients with the dosimetric compliance criteria of the new in house phase I trial of high dose rate (HDR) brachytherapy combined with stereotactic body radiotherapy (SBRT) for intermediate risk prostate cancer patients. Methods: Ten prostate cancer patients were treated using this trial. They received one fraction of HDR to 15Gy, followed by external beam(EB) boost of 3.2Gy(Level 1, five patients) or 3.94Gy(level 2, five patients) per fraction for 10 or 7 fractions, respectively, both equivalent to EB treatments of 113.5Gy in 2Gy fractions. The EB plans were either IMRT or VMAT plans. DVH analysis was performed to verify the adherence of treatment plans to the dosimetric criteria of the trial. Results: For Level 1 patients, target coverage were adequate, with CTV V32Gy(%) of 99.0±1.0 (mean ± 1 standard deviation), and PTV V31Gy(%) of 99.6±0.3. PTV V32.9Gy(%) is 1.4±3.1 and PTVmax is 32.9±0.2Gy. Rectum, bladder and femoral heads sparing were well within protocol criteria. For Level 2 patients, CTV V27.6Gy(%) is 98.7±1.8; PTV V26.7Gy(%) is 99.0±1.4. PTV V28.4Gy(%) is 1.3±1.4, with three patients having minor deviation from protocol. Again critical structures were spared compliant to the protocol. The analysis of HDR plans show similar results, with adequate dose coverage to the prostate and sparing of critical structures including urethra and rectum. V100(%) and V90(%) of prostate are 96.0±1.1 and 98.9±0.5. Urethra D10(%) is 113.1±2.9. Rectum V80(cc) is 1.4±0.5. Hotspot in prostate is substantially higher than what the protocol specifies. But the criteria for hotspot are only guidelines, serving to lower the dose to urethra . Conclusion: This new high biological equivalent dose prostate trial has been carried out successfully for ten patients. Based on dosimetric analysis, all HDR and external plans were compliant to the protocol criteria, with only minor deviations.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2016

A massive molecular gas reservoir in the z = 2.221 type-2 quasar host galaxy SMM J0939+8315 lensed by the radio galaxy 3C220.3

We report the detection of CO(J = 3 → 2) line emission in the strongly lensed submillimeter galaxy (SMG) SMM J0939+8315 at z = 2.221, using the Combined Array for Research in Millimeter-wave Astronomy. SMM J0939+8315 hosts a type-2 quasar, and is gravitationally lensed by the radio galaxy 3C220.3 and its companion galaxy at z = 0.685. The 104 GHz continuum emission underlying the CO line is detected toward 3C220.3 with an integrated flux density of S{sub cont} = 7.4 ± 1.4 mJy. Using the CO(J = 3 → 2) line intensity of I{sub CO(3-2)} = (12.6 ± 2.0) Jy km s{sup −1}, we derive a lensing- and excitation-corrected CO line luminosity of L{sub CO(1−0)}{sup ′} = (3.4 ± 0.7) × 10{sup 10} (10.1/μ{sub L}) K km s{sup −1} pc{sup 2} for the SMG, where μ{sub L} is the lensing magnification factor inferred from our lens modeling. This translates to a molecular gas mass of M{sub gas} = (2.7 ± 0.6) × 10{sup 10} (10.1/μ{sub L}) M{sub ⊙}. Fitting spectral energy distribution models to the (sub)-millimeter data of this SMG yields a dust temperature of T = 63.1{sub −1.3}{sup +1.1} K, a dust mass of M{sub dust} = (5.2 ± 2.1) × 10{sup 8} (10.1/μ{sub L}) M{sub ⊙}, and a total infrared luminosity of L{sub IR} = (9.1 ± 1.2) ×10{sup 12} (10.1/μ{sub L}) L{sub ⊙}. We find that the properties of the interstellar medium of SMM J0939+8315 overlap with both SMGs and type-2 quasars. Hence, SMM J0939+8315 may be transitioning from a starbursting phase to an unobscured quasar phase as described by the “evolutionary link” model, according to which this system may represent an intermediate stage in the evolution of present-day galaxies at an earlier epoch.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRS1976

Equilibrium and disequilibrium chemistry of adiabatic, solar-composition planetary atmospheres

The impact of atmospheric and cloud-structure models on the nonequilibrium chemical behavior of the atmospheres of the Jovian planets is discussed. Quantitative constraints on photochemical, lightning, and charged-particle production of organic matter and chromophores are emphasized whenever available. These considerations imply that inorganic chromophore production is far more important than that of organic chromophores, and that lightning is probably a negligibly significant process relative to photochemistry on Jupiter. Production of complex molecules by gas-phase disequilibrium processes on Saturn, Uranus, and Neptune is severely limited by condensation of even simple intermediates.

Lewis, J. S.↗

NASA NTRS1978

Evolution of a nitrogen atmosphere on Titan

Photochemical calculations indicate that if NH3 outgassed from Titan it should have been converted to a dense N2 atmosphere during the lifetime of the satellite. A crucial step in the process involves a gas phase reaction of N2H4 with H. The most favorable conditions for this step would be the intermediate production of a CH4-H2 greenhouse capable of raising the gas temperature to 150 K. Subsequently about 20 bars of N2 could have evolved. The pressure-induced opacity of 20 bars of N2 should suffice to explain the recently measured 200 K surface temperature. Unlike the situation on Jupiter, NH3 is not recycled on Titan by reactions involving N2 or N2H4. This may explain the failure of recent attempts to detect NH3 in the upper atmosphere of Titan.

Atreya, S. K.↗

NASA NTRS1990

Radiative magnetized thermal conduction fronts

The evolution of plane-parallel magnetized thermal conduction fronts in the interstellar medium (ISM) was studied. Separating the coronal ISM phase and interstellar clouds, these fronts have been thought to be the site of the intermediate-temperature regions whose presence was inferred from O VI absorption-line studies. The front evolution was followed numerically, starting from the initial discontinuous temperature distribution between the hot and cold medium, and ending in the final cooling stage of the hot medium. It was found that, for the typical ISM pressure of 4000 K/cu cm and the hot medium temperature of 10 to the 6th K, the transition from evaporation to condensation in a nonmagnetized front occurs when the front thickness is 15 pc. This thickness is a factor of 5 smaller than previously estimated. The O VI column densities in both evaporative and condensation stages agree with observations if the initial hot medium temperature Th exceeds 750,000 K. Condensing conduction fronts give better agreement with observed O VI line profiles because of lower gas temperatures.

Borkowski, Kazimierz J.↗

NASA NTRS1989

Response of a mouse hybridoma cell line to heat shock, agitation, and sparging

A mouse hybridoma cell line is used as a model system for studying the effect of environmental stress on attachment-independent mammalian cells. The full time course of recovery for a mouse hybridoma cell line from both a mild and intermediate heat shock is examined. The pattern of intracellular synthesis is compared for actively growing, log phase cells and nondividing, stationary phase cells.

Passini, Cheryl A.↗

NASA NTRS1993

Laboratory simulated hydrothermal alteration of sedimentary organic matter from Guaymas Basin, Gulf of California

High temperature alteration of sedimentary organic matter associated with marine hydrothermal systems involves complex physical and chemical processes that are not easily measured in most natural systems. Many of these processes can be evaluated indirectly by examining the geochemistry of the hydrothermal system in the laboratory. In this investigation, an experimental organic geochemical approach to studying pyrolysis of sedimentary organic matter is applied to the hydrothermal system in the Guaymas Basin, Gulf of California. A general survey of hydrothermal oils and extractable organic matter (bitumen) in hydrothermally altered sediments identified several homologous series of alkanones associated with a high temperature hydrothermal origin. The alkanones range in carbon number from C11 to C30 with no carbon number preference. Alkan-2-ones are in highest concentrations, with lower amounts of 3-, 4-, 5- (and higher) homologs. The alkanones appear to be pyrolysis products synthesized under extreme hydrothermal conditions. Hydrous pyrolysis and confinement pyrolysis experiments were performed to simulate thermally enhanced diagenetic and catagenetic changes in the immature sedimentary organic matter. The extent of alteration was measured by monitoring the n-alkanes, acyclic isoprenoids, steroid and triterpenoid biomarkers, polycyclic aromatic hydrocarbons and alkanones. The results were compared to bitumen extracts from sediments which have been naturally altered by a sill intrusion and accompanied hydrothermal fluid flow. These pyrolysis experiments duplicated many of the organic matter transformations observed in the natural system. Full hopane and sterane maturation occurred after 48 hr in experiments at 330 deg C with low water/rock mass ratios (0.29). A variety of radical and ionic reactions are responsible for the organic compound conversions which occur under extreme hydrothermal conditions. Short duration pyrolysis experiments revealed that a portion of the hydrocarbons generated from kerogen was observed to go through alkene intermediates, and the rate of alkene isomerization was influenced by the ionic strength and catalytic mineral phases. Confinement of the organic pyrolysate to the bulk sediment accelerated the rates of the biomarker epimerization reactions, suggesting that these reactions are influenced strongly by the association of the inorganic matrix, and that the relative rates of some ionic and radical reactions can be influenced by the water/rock ratio during the pyrolysis experiments.

Leif, Roald N.↗

NASA NTRS2009

Joint Carrier-Phase Synchronization and LDPC Decoding

A method has been proposed to increase the degree of synchronization of a radio receiver with the phase of a suppressed carrier signal modulated with a binary- phase-shift-keying (BPSK) or quaternary- phase-shift-keying (QPSK) signal representing a low-density parity-check (LDPC) code. This method is an extended version of the method described in Using LDPC Code Constraints to Aid Recovery of Symbol Timing (NPO-43112), NASA Tech Briefs, Vol. 32, No. 10 (October 2008), page 54. Both methods and the receiver architectures in which they would be implemented belong to a class of timing- recovery methods and corresponding receiver architectures characterized as pilotless in that they do not require transmission and reception of pilot signals. The proposed method calls for the use of what is known in the art as soft decision feedback to remove the modulation from a replica of the incoming signal prior to feeding this replica to a phase-locked loop (PLL) or other carrier-tracking stage in the receiver. Soft decision feedback refers to suitably processed versions of intermediate results of iterative computations involved in the LDPC decoding process. Unlike a related prior method in which hard decision feedback (the final sequence of decoded symbols) is used to remove the modulation, the proposed method does not require estimation of the decoder error probability. In a basic digital implementation of the proposed method, the incoming signal (having carrier phase theta theta (sub c) plus noise would first be converted to inphase (I) and quadrature (Q) baseband signals by mixing it with I and Q signals at the carrier frequency [wc/(2 pi)] generated by a local oscillator. The resulting demodulated signals would be processed through one-symbol-period integrate and- dump filters, the outputs of which would be sampled and held, then multiplied by a soft-decision version of the baseband modulated signal. The resulting I and Q products consist of terms proportional to the cosine and sine of the carrier phase cc as well as correlated noise components. These products would be fed as inputs to a digital PLL that would include a number-controlled oscillator (NCO), which provides an estimate of the carrier phase, theta(sub c).

Simon, Marvin↗

NASA NTRS1987

Turbulence as a contributor to intermediate energy storage during solar flares

Turbulence is considered as a method for converting the energy observed as mass motions during the impulsive phase into thermal energy observed during the gradual phase of solar flares. The kinetic energy of the large-scale eddies driven by the upflowing material continuously cascades to smaller scale eddies until viscosity is able to convert it into thermal energy. The general properties of steady state, homogeneous, fluid turbulence is a nonmagnetic plasma and the properties of turbulent decay are reviewed. The time-dependent behavior of the velocities and energies observed by the X-Ray Polychromator (XRP) instrument on the SMM during the November 5, 1980 flare are compared with the properties of turbulence. This study indicates that turbulence may play a role in flare energies and may account for a fraction of the total amount of thermal energy observed during the gradual phase. The rate at which the observed flare velocities decrease is consistent with the decay of turbulent energy but may be too rapid to account for the entire time delay between the impulsive and gradual phases.

Bornmann, P. L.↗

NASA NTRS2021

The Near and Intermediate Wake of a Thick Flat Plate with a Circular Trailing Edge

The near and intermediate wake regions of a thick flat plate with a circular trailing edge (TE) are investigated with a direct numerical simulation (DNS). The focus is on the region x/D < 43.0(D is the diameter of the TE). The upper and lower separating boundary layers are both turbulent and are statistically identical; the resulting wake is symmetric in the mean. The present study is a continuation of an earlier investigation (Case AX). The earlier research dealt with shed vortex structure, in particular the persistence of the coherence of these vortices with increasing streamwise distance (except for infrequent, random disruption/rupture). In addition, across-centerline movement (ACM)of shed vortices, that is prevalent past x/D = 20.0 in a cylinder case at a comparable Reynolds number, was found to be essentially absent in Case AX. In the present investigation, an underlying cause for the occasional disruption/rupture of shed vortices is explored. Strong interactions between subsequent shed vortices in the trailing edge region is found to be an important contributor to this phenomenon. The distributions of phase-averaged streamwise and cross-stream components of intensity and the corresponding budget terms in the near wake are compared with those obtained in the intermediate wake here. In addition, the main features of the distribution of the phase-averaged velocity pressure-gradient term are compared with those of the production term, for the two intensity components. Except for a change in sign, the important features in the two budget terms are qualitatively similar for both components.

Direct Numerical Simulations of Flat Plate Wake↗

DOE OSTI2025

In-Situ Atomic-Scale Revelation of Amorphous Metallic Iron Formation during Hydrogen-Driven Reduction of Iron Oxides

The transition to hydrogen as a green reductant in metal production is critical for decarbonizing the metallurgical industry, yet atomic-scale mechanisms governing reduction pathways and phase evolution remain unresolved. Using in-situ environmental transmission electron microscopy, we identify a hidden pathway that reveals dynamic formation of amorphous metallic iron (Fe) during the hydrogen-driven reduction of ferrous oxides of Fe 3 O 4 and FeO. Real-time imaging uncovers three coexisting transformation routes: (i) Fe 3 O 4 → FeO, (ii) Fe 3 O 4 → amorphous Fe, and (iii) FeO → amorphous Fe. The resulting amorphous Fe exhibits fluid-like mobility, enabling its rapid aggregation and crystallization into core-shell nanostructures, with a crystalline core enveloped by an amorphous shell. Complementary ab initio molecular dynamics simulations trace the amorphous Fe formation to interfacial strain at the metal/oxide interfaces, where large lattice mismatches destabilize the metal lattice during initial metallization. This interplay between thermodynamics and kinetics governs phase evolution: thermodynamics favors a self-limiting amorphous Fe overlayer, while rapid oxide reduction kinetics drives amorphous overgrowth. Our findings demonstrate that amorphous intermediates bypass rate-limiting crystalline steps, providing mechanistic insights to optimize H 2 -based processes for sustainable steelmaking. In conclusion, these insights bridge the gap between macroscopic process engineering and atomic-scale dynamics, with broader implications for catalysis and nanostructured material synthesis, where oxide reduction pathways critically shape functional phases and microstructures.

36 MATERIALS SCIENCE↗

DOE OSTI2013

Revisiting dynamics near a liquid-liquid phase transition in Si and Ga: The fragile-to-strong transition

Using molecular dynamics simulations we analyze the dynamics of two atomic liquids that display a liquid-liquid phase transition (LLPT): Si described by the Stillinger-Weber potential and Ga as modeled by the modified embedded-atom model. In particular, our objective is to investigate the extent to which the presence of a dip in the self-intermediate scattering function is a manifestation of an excess of vibrational states at low frequencies and may be associated with a fragile-to-strong transition (FTST) across the LLPT, as suggested recently. Our results suggest a somewhat different picture. First, in the case of Ga we observe the appearance of an excess of vibrational states at low frequencies, even in the absence of the appearance of a dip in the self-intermediate scattering function across the LLPT. Second, studying the behavior of the shear viscosities traversing the LLPTs we find that both substances are fragile in character above and below their respective LLPT temperatures. Instead of a FTST in an absolute sense these findings are more in line with a view in which the LLPTs are accompanied by a transition from a more fragile to a less fragile liquid. Furthermore, we do not find this transition to correlate with the presence of a dip in the intermediate scattering function.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗