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DOE OSTI2019

Energy Decomposition Analysis for Interactions of Radicals: Theory and Implementation at the MP2 Level with Application to Hydration of Halogenated Benzene Cations and Complexes between CO 2 -· and Pyridine and Imidazole

To study intermolecular interactions involving radicals at the correlated level, the energy decomposition analysis scheme for second-order Møller-Plesset perturbation theory based on absolutely localized molecular orbitals (ALMO-MP2-EDA) is generalized to unrestricted and restricted open-shell MP2. The benefit of restricted open-shell MP2 is that it can provide accurate binding energies for radical complexes where density functional theory can be error-prone due to delocalization errors. As a model application, the open-shell ALMO-MP2-EDA is applied to study the first solvation step of halogenated benzene radical cations, where both halogen- and hydrogen-bonded isomers are possible. We determine that the lighter halogens favor the hydrogen-bonded form, while the iodine-substituted species prefers halogen bonding due to larger polarizability and charge transfer at the halogen. As a second application, relevant to the activation of CO 2 in photoelectrocatalysis, complexes of CO 2 -· interacting with both pyridine and imidazole are analyzed with ALMO-MP2-EDA. The results reveal the importance of charge transfer into the π* orbital of the heterocycle in controlling the stability of the carbamate binding mode, which is favored for pyridine but not for imidazole.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Hydration Free Energies of Polypeptides from Popular Implicit Solvent Models versus All-Atom Simulation Results Based on Molecular Quasichemical Theory

Calculating the hydration free energy of a macromolecule in all-atom simulations has long remained a challenge, necessitating the use of models wherein the effect of the solvent is captured without explicit account of solvent degrees of freedom. This situation has changed with developments in the molecular quasi-chemical theory (QCT)-an approach that enables calculation of the hydration free energy of macromolecules within all-atom simulations at the same resolution as is possible for small molecular solutes. The theory also provides a rigorous and physically transparent framework to conceptualize and model interactions in molecular solutions and thus provides a convenient framework to investigate the assumptions in implicit solvent models. In this study, we compare the results using molecular QCT versus predictions from EEF1, ABSINTH, and GB/SA implicit solvent models for polyglycine and polyalanine solutes covering a range of chain lengths and conformations. The hydration free energies or the differences in hydration free energies between conformers obtained from the implicit solvent models do not agree with explicit solvent results, with the deviations being largest for the group additive EEF1 and ABSINTH models. GB/SA does better in capturing the qualitative trends seen in explicit solvent results. Finally, analysis founded on QCT reveals the critical importance of the cooperativity of hydration that is inherent in the hydrophilic and hydrophobic contributions to hydration-physics that is not well captured in additive models but somewhat better accounted for by means of a dielectric in the GB/SA approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Molecular Theory of Hydration at Different Temperatures

Solvation plays an important role in diverse chemical processes ranging from reaction kinetics to molecular recognition, solubility, and phase separations. Despite a long-history of theoretical exploration, quantitative prediction of solvation remains a theoretical challenge without relying on the macroscopic properties of the solvent as an input. Here we present a molecular density functional theory that provides a self-consistent description of the solvation structure and thermodynamic properties of small organic molecules in liquid water at different temperatures. Based on the solute configuration and force-field parameters generated from first-principles calculations, the theoretical predictions are found in good agreement with experimental data for the hydration free energies of 197 organic molecules in a temperature range from 0 to 40 °C. In addition to calibration with experimental results, the theoretical predictions are compared with recent molecular dynamics simulations for the hydration of five highly explosive nitrotoluenes. Lastly, this work demonstrates the potential of the classical density functional theory for high-throughput prediction of solvation properties over a broad range of temperatures.

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

Role of Solute Attractive Forces in the Atomic-Scale Theory of Hydrophobic Effects

The role that van der Waals (vdW) attractive forces play in the hydration and association of atomic hydrophobic solutes such as argon (Ar) in water is reanalyzed using the local molecular field (LMF) theory of those interactions. In this problem, solute vdW attractive forces can reduce or mask hydrophobic interactions as measured by contact peak heights of the ArAr correlation function compared to reference results for purely repulsive core solutes. Nevertheless, both systems exhibit a characteristic hydrophobic inverse temperature behavior in which hydrophobic association becomes stronger with increasing temperature through a moderate temperature range. The new theoretical approximation obtained here is remarkably simple and faithful to the statistical mechanical LMF assessment of the necessary force balance. In conclusion, our results extend and significantly revise approximations made in a recent application of the LMF approach to this problem and, unexpectedly, support a theory of nearly 40 years ago.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Hole Polaron Transport in Bismuth Vanadate BiVO 4 from Hybrid Density Functional Theory

In this paper, we address the chemical character and the mobility of hole polarons in BiVO 4 (BVO). Two distinct structures for hole polarons in BVO have been reported in the literature to date. “Standard” hybrid density functional theory (DFT) calculations have predicted hole polarons to be (BiO 8 ) dodecahedron-centered polarons, while Hubbard U-DFT (DFT + U) calculations have predicted single oxygen atom-centered polarons. Resolving these contrasting findings is critical to validate theory in materials research. We investigated the structure of hole polarons in BVO using hybrid DFT with varying fractions (α) of the exact exchange interaction that enters hybrid functionals. For values of the fraction α, from α = 0.25 to α = 0.45, we obtained both structures, the h + (BiO 8 ) hole structure and the h + (O) hole structure. For the smaller values of α, the h + (BiO 8 ) structure is lower in energy, while for the larger values of α, the h+(O) structure is more stable. The piece-wise linearity of DFT energies E(q) with respect to a point defect charge q is maintained satisfactorily in all cases, although the deviation is the smallest for hybrid DFT with a small exact exchange fraction. For α = 0.25, we determined the diffusivity of h + (BiO 8 ) holes from the Marcus/Holstein two-state model. The activation barrier for Bi-to-Bi hops (ΔG # ~76 meV) and mobility (μ ~0.029 cm2 V –1 s –1 ) are found to be in close agreement with the published THz experimental data (ΔG # ~90 meV and μ exp ~0.02 cm2 V –1 s –1 , respectively). In h + (BiO 8 ) structures, nearly 25% of the hole charge and unpaired spin reside on the Bi atom and the rest is divided among the eight O atoms. The hole is best described as a Bi-centered hole, rather than a Bi 6s hole. In contrast, in h + (O) structures, about 75% of the unpaired spin population resides on the O atom. These findings suggest that if one wishes to resolve this theoretical dichotomy, there remains a need for further experimental characterization of hole polarons in BVO with techniques that could identify the oxidation state of Bi and O atoms in operando conditions and help validate theoretical results of structure and transport.

14 SOLAR ENERGY↗
DOE OSTI2022

Characterization of Lanthanum Monazite Surface Chemistry and Crystal Morphology through Density Functional Theory and Experimental Approaches

Monazite is a rare earth element (REE)-containing mineral that consists of (REE)PO 4 formal units and is one of the most important sources of these critical materials. The concentration of REEs from mined monazite ore often involves froth flotation, which is a beneficiation process that enhances the efficiency of downstream processing. The effectiveness of froth flotation is largely governed by the ability of collector agents to selectively bind to monazite particles. Thus, a molecular-level understanding of monazite interfacial chemistry is integral to the design of effective collector agents. To address this need, we performed density functional theory (DFT) calculations and a variety of experimental techniques to characterize La-monazite and elucidate its crystal morphology. Interestingly, we find minimal differences in the predicted morphologies of La-monazite for hydrous and anhydrous environments, which are largely dominated by low-index facets (e.g., {110}, {100}, and {010}). Indexing of synthesized La-monazite crystals via X-ray diffraction also uncovers {110} and {100} as the predominant facets. The average surface energies of 0% and 100% water coverage La-monazite crystals were predicted to be 0.87 and 0.76 J/m 2 , respectively, while calorimetry suggests values of 1.30 and 1.15 J/m 2 , respectively. The apparent discrepancies between the theoretical and experimental values are expected and attributed to defects present in physical crystals, in contrast to the perfect mineral surfaces in simulations. The difference in surface energy between the 0% and 100% water coverage morphologies predicted by theory is consistent with the value measured via calorimetry. DFT reveals a wide range of adsorption energies for water across the studied facets, but in all cases, water is predicted to strongly bind to monazite surfaces with an average adsorption energy of -92.7 kJ/mol for a La-monazite single crystal. Finally, this study provides the groundwork necessary for the rational design of froth flotation collector agents by granting molecular-level insight into the predominant facets of monazite.

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

Excitons in Hematite Fe 2 O 3 : Short-Time Dynamics from TD-DFT and Non-Adiabatic Dynamics Theories

We present a first-principles study of the short-time dynamics of excitons in hematite Fe 2 O 3 . We used time-dependent density functional theory (TD-DFT) with an underlying DFT+U treatment of electron interactions to characterize the electronic structure of excitons and nonadiabatic molecular dynamics theory (NA-MD) to determine their recombination (electronic ground-state recovery) and relaxation dynamics. Decoherence-corrected trajectory surface hopping approaches in NA-MD simulations yielded recovery times of ~1.1 to 1.8 ns and “higher-lying” exciton relaxation times of ~60 to 70 fs, in accord with experimentally derived lifetimes. With hematite phonons in the range of ~100 to 700 cm –1 , higher-lying excitons relax within one or two oscillations of the phonons before getting trapped into an electron–hole pair Exc-3 structure on the first excited state potential energy surface. This structure resembles already a pair of polarons (electron polaron plus hole polaron) with associated lattice distortions three (3) basal planes away. On longer time scales, the electron–hole bipolaronic pair hops to structures Exc-5, then Exc-7, then Exc-9, ... with the electron polaron and hole polaron separated by 5, 7, 9, ... basal planes in a process of charge separation. The largest frequency phonon ~672 cm –1 for the Exc-3 exciton structure is associated with the electron polaron moiety of the exciton. This phonon is a good candidate for giving rise to the recently observed and reported postexcitation transient IR absorption peak.

36 MATERIALS SCIENCE↗
DOE OSTI2025

ReaxFF Parameter Set for Boron Clusters and Icosahedral Boron Crystals: Comparison with Density Functional Theory and Machine-Learning Potentials

Icosahedral boron materials, which include regular icosahedra of 12 boron atoms have gained increasing attention due to their potential applications as superhard materials, semiconductors, and energy storage media. However, the synthesis of high quality crystals of these materials has been a major barrier to the development of these applications. To enable computational prediction of synthesis conditions yielding high-quality icosahedral boron crystals, herein we tested and refined a set of ReaxFF parameters for the nucleation and growth of such crystals. We focused on matching the relative energies of small boron clusters obtained by density functional theory since such small clusters and similar motifs are likely present in crystal nuclei and at the interface of growing crystals. Using a training set of B 80 clusters, including a low-energy core–shell structure containing a B 12 icosahedron core and a high-energy single-shell structure produced in preliminary ReaxFF simulations, the ReaxFF parameter set was refined to better reproduce energies calculated by density functional theory (DFT). Among existing ReaxFF parameter sets and the machine-learning interatomic potentials MACE-MP-0, MACE-MP-0b3, MACE-MPA-0, PFP v7.0.0, and SevenNet-MF-ompa, only our new parameter set and PFP v7.0.0 correctly ranked these B 80 clusters. This refinement led to improved agreement with DFT for a test set of 58 clusters consisting of 8–103 boron atoms. Furthermore, our refined parameter set yielded greater local icosahedral structure than the previously existing ReaxFF parameter set for larger scale simulations of crystallization from supercooled liquid boron. Additionally, simulations of solid boron in contact with molten nickel using our refined ReaxFF parameters yielded a boron solubility value that agrees moderately well with experimental expectations, while the previous boron parameters gave a value that was much too low.

boron↗
DOE OSTI2018

Identifying the Thermal Decomposition Mechanism of Guaiacol on Pt(111): An Integrated X-ray Photoelectron Spectroscopy and Density Functional Theory Study

Using a concerted effort from both experiment and theory, we determine the thermal decomposition mechanism for guaiacol on Pt(111), a reaction of interest in the area of bio-oil upgrading. This work serves as a demonstration of the power of combining in situ temperature-programmed X-ray photoelectron spectroscopy cos (TPXPS) and density functional theory (DFT) to elucidate complex reaction mechanisms occurring on heterogeneous surfaces. At low temperature (230 K), guaiacol was found to chemisorb with the aromatic ring parallel to the Pt(111) surface with five distinct carbon species and three oxygen species. As the temperature was increased, TPXPS showed several significant changes to the surface species. The increase in the species associated with the decomposition of the functional groups of guaiacol is followed by their subsequent disappearance and an increase in the nonaromatic carbon signal. On the basis of an energetic analysis of the various mechanisms using DFT, along with the comparison of the experimentally and theoretically derived core-level binding energies, we determined that guaiacol's decomposition mechanism occurs via the dehydrogenation of both the methyl and hydroxyl functional groups, followed by demethylation of the CH2 or CH group to form 1,2-benzoquinone. Further heating to above 375 K likely breaks the aromatic ring and results in the rapid formation and desorption of CO, accounting for the disappearance of the 0 is signal above 450 K These results show that a knowledgeable application of TPXPS and DFT can result in the quantitative identification of surface species during complex reactions, providing insight useful for the design of future heterogeneous surfaces.

Hensley, Alyssa J. R. (ORCID:0000000273821286)↗
DOE OSTI2018

Predicting Surface Energies and Particle Morphologies of Boehmite (y-AlOOH) from Density Functional Theory

Particle morphology is an important property affecting the reactivity of solid phases. The aluminum oxyhydroxide boehmite (?-AlOOH) is one example for which particle morphology has relevance to geochemistry, environmental management, and catalysis. Morphologies can be predicted from surface and attachment energies obtained from electronic structure calculations but the dependence of these predictions on the level of theory and complexity of the physics involved has been overlooked. Density functional theory calculations were therefore performed for a wide range of exchange-correlation (XC) functionals, including a hybrid functional, to calculate the energetics of the four main low-index surfaces of boehmite both in vacuum and with a water monolayer adsorbed. The approximation used for describing core electrons, the size of the plane-wave basis set, and the need for dispersion corrections were also investigated. The results highlight the critical need for converged plane-wave basis sets to obtain accurate surface energies as well as the strong influence the XC functional can have on surface energies and water adsorption energies. The predicted morphologies were compared to particle morphologies obtained from a variety of synthesis routes both carried out in this work and published in the literature. The comparison showed that, at basic pH, growth morphologies dominated at low temperatures and short time periods whereas equilibrium morphologies were achieved as the temperature and/or aging time increased, which could be explained by the slow stacking growth mode of boehmite along the [010] direction. Finally, calorimetry experiments are often used to derive surface energies, but excess water on hydrophilic surfaces can add significant uncertainty. An approach for correcting the surface energetics obtained by calorimetry using electronic structure calculations is presented.

Prange, Micah P.↗
DOE OSTI2023

Local Excitations of a Charged Nitrogen Vacancy in Diamond with Multireference Density Matrix Embedding Theory

Here, we investigate the negatively charged nitrogen-vacancy center in diamond using periodic density matrix embedding theory (pDMET). To describe the strongly correlated excited states of this system, the complete active space self-consistent field (CASSCF) followed by n-electron valence state second-order perturbation theory (NEVPT2) was used as the impurity solver. Since the NEVPT2-DMET energies show a linear dependence on the inverse of the size of the embedding subspace, we performed an extrapolation of the excitation energies to the nonembedding limit using a linear regression. The extrapolated NEVPT2-DMET first triplet–triplet excitation energy is 2.31 eV and that for the optically inactive singlet–singlet transition is 1.02 eV, both in agreement with the experimentally observed vertical excitation energies of ∼2.18 eV and ∼1.26 eV, respectively. This is the first application of pDMET to a charged periodic system and the first investigation of the NV – defect using NEVPT2 for periodic supercell models.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Broken Symmetry Optical Transitions in (6,5) Single-Walled Carbon Nanotubes Containing sp 3 Defects Revealed by First-Principles Theory

We present a first-principles many-body perturbation theory study of nitrophenyl-doped (6,5) single-walled nanotubes (SWCNTs) to understand how sp 3 doping impacts the excitonic properties. sp 3 -doped SWCNTs are promising as a class of optoelectronic materials with bright tunable photoluminescence, long spin coherence, and single-photon emission (SPE), motivating the study of spin excitations. We predict that the dopant results in a single unpaired spin localized around the defect site, which induces multiple low-energy excitonic peaks. By comparing optical absorption and photoluminescence from experiment and theory, we identify the transitions responsible for the red-shifted, defect-induced E 11 * peak, which has demonstrated SPE for some dopants; the presence of this state is due to both the symmetry-breaking associated with the defect and the presence of the defect-induced in-gap state. Furthermore, we find an asymmetry between the contribution of the two spin channels, suggesting that this system has potential for spin-selective optical transitions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Integrating Density Functional Theory Calculations with Vibrational and Nuclear Magnetic Resonance Spectroscopy

This review focuses on the complementary nature of density functional theory calculations and spectroscopic studies related to cellulose and its interactions within plant cell walls (PCWs). The complexity, structural disorder, and nanoscale nature of PCWs make them difficult to analyze and understand, but advances in sum-frequency generation and nuclear magnetic resonance spectroscopies as well as in density functional theory have made it possible to elucidate structure not observable previously. Combined with other techniques such as wide-angle X-ray scattering and neutron diffraction, details of PCW components (e.g., cellulose, lignin, pectin) and their interactions with one another can be elucidated. Furthermore, these techniques provide new insight into biological and biochemical studies and provide a basis for creating improved models of the PCWs.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Substitution Reactions in the Pyrolysis of Acetone Revealed through a Modeling, Experiment, Theory Paradigm

The development of high-fidelity mechanisms for chemically reactive systems is a challenging process that requires the compilation of rate descriptions for a large and somewhat ill-defined set of reactions. The present unified combination of modeling, experiment, and theory provides a paradigm for improving such mechanism development efforts. Here we combine broadband rotational spectroscopy with detailed chemical modeling based on rate constants obtained from automated ab initio transition state theory-based master equation calculations and high-level thermochemical parametrizations. Broadband rotational spectroscopy offers quantitative and isomer-specific detection by which branching ratios of polar reaction products may be obtained. Using this technique, we observe and characterize products arising from H atom substitution reactions in the flash pyrolysis of acetone (CH 3 C(O)CH 3 ) at a nominal temperature of 1800 K. The major product observed is ketene (CH 2 CO). Minor products identified include acetaldehyde (CH 3 CHO), propyne (CH 3 CCH), propene (CH 2 CHCH 3 ), and water (HDO). Literature mechanisms for the pyrolysis of acetone do not adequately describe the minor products. The inclusion of a variety of substitution reactions, with rate constants and thermochemistry obtained from automated ab initio kinetics predictions and Active Thermochemical Tables analyses, demonstrates an important role for such processes. Furthermore, the pathway to acetaldehyde is shown to be a direct result of substitution of acetone's methyl group by a free H atom, while propene formation arises from OH substitution in the enol form of acetone by a free H atom.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Revisiting Understanding of Electrochemical CO 2 Reduction on Cu(111): Competing Proton-Coupled Electron Transfer Reaction Mechanisms Revealed by Embedded Correlated Wavefunction Theory

Copper (Cu) electrodes, as the most efficacious of CO 2 reduction reaction (CO 2 RR) electrocatalysts, serve as prototypes for determining and validating reaction mechanisms associated with electrochemical CO 2 reduction to hydrocarbons. As in situ electrochemical mechanism determination by experiments is still out of reach, such mechanistic analysis typically is conducted using density functional theory (DFT). The semilocal exchange-correlation (XC) approximations most often used to model such catalysis unfortunately engender a basic error: predicting the wrong adsorption site for CO (a key CO 2 RR intermediate) on the most ubiquitous facet of Cu, namely, Cu(111). This longstanding inconsistency casts lingering doubt on previous DFT predictions of the attendant CO 2 RR kinetics. Here, we apply embedded correlated wavefunction (ECW) theory, which corrects XC functional error, to study the CO 2 RR on Cu(111) via both surface hydride (*H) transfer and proton-coupled electron transfer (PCET). We predict that adsorbed CO (*CO) reduces almost equally to two intermediates, namely, hydroxymethylidyne (*COH) and formyl (*CHO) at –0.9 V vs the RHE. In contrast, semilocal DFT approximations predict a strong preference for *COH. With increasing applied potential, the dominance of *COH (formed via potential-independent surface *H transfer) diminishes, switching to the competitive formation of both *CHO and *COH (both formed via potential-dependent PCET). Furthermore, our results also demonstrate the importance of including explicitly modeled solvent molecules in predicting electron-transfer barriers and reveal the pitfalls of overreliance on simple surface *H transfer models of reduction reactions.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2021

A Theory-Guided X-ray Absorption Spectroscopy Approach for Identifying Active Sites in Atomically Dispersed Transition-Metal Catalysts

Atomically dispersed supported metal catalysts offer new properties and the benefits of maximized metal accessibility and utilization. The characterization of these materials, however, remains challenging. Using atomically dispersed platinum supported on crystalline MgO (chosen for its well-defined bonding sites) as a prototypical example, we demonstrate in this work how systematic density functional theory calculations for assessing all the potentially stable platinum sites, combined with automated analysis of extended X-ray absorption fine structure (EXAFS) spectra, leads to unbiased identification of isolated, surface-enveloped platinum cations as the catalytic species for CO oxidation. The catalyst has been characterized by atomic-resolution imaging and EXAFS and high-energy resolution fluorescence detection X-ray absorption near edge spectroscopy. The proposed platinum sites are in agreement with experiment. This theory-guided workflow leads to rigorously determined structural models and provides a more detailed picture of the structure of the catalytically active site than what is currently possible with conventional EXAFS analyses. As this approach is efficient and agnostic to the metal, support, and catalytic reaction, we posit that it will be of broad interest to the materials characterization and catalysis communities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electron Transfer Theory Elucidates the Hidden Role Played by Triethylamine and Triethanolamine during Photocatalysis

Triethylamine (TEA) and triethanolamine (TEOA) are renowned, in part, for their ability to reductively quench excited states by outer-sphere electron transfer with vast and still growing applications as sacrificial electron donors for photocatalytic systems. Upon amine oxidation, the resulting TEA •+ and TEOA •+ radical cations undergo proton transfer (or hydrogen atom transfer), resulting in the formation of a chemical reductant that has an α-carbon centered radical adjacent to the nitrogen center (TEA • and TEOA • ). In this contribution, we have electrochemically and spectroscopically characterized a set of electron acceptors which, upon accepting an electron, are a series of photocatalysts, [ReCl(R 1 R 2 -bpy)(CO) 3 ] •– , where R 1 and R 2 are electron-donating and electron-withdrawing groups in the 4,4′- and 5,5′-positions on the bipyridyl ligand. Here, we substantiated the formation of the electron donors, TE(O)A • , by spin trapping electron paramagnetic resonance spectroscopy, where TE(O)A • reacts with 2,4,6-tri-tert-butylnitrosobenzene to generate N-centered and O-centered radical adducts. Having established the chemical behaviors of the electron acceptors and donors individually, the electron transfer rate constants were determined across a 1.43 V range in driving force. The redox potential of TEA • was benchmarked to within ±80 mV on an absolute scale in V vs Fc + /Fc in CH 3 CN by using an empirical rate vs free-energy correlation, electron transfer theory, and density functional theory calculations. The equilibrium potentials for TEA • and TEOA • were determined to be −1.98 V and −1.76 V, respectively. Based on the kinetic and thermochemical analysis presented for TEA • and TEOA • , these transient radicals can be broadly considered strong homogeneous chemical reductants within the wider context of photoredox potentials. Thus, this work clarifies a frequently unnoticed secondary function for these sacrificial electron donors during photocatalysis and rationalizes the possibility of a one-photon/two-electron conversion process that is dependent on the free-energy exchange between TE(O)A • and photocatalysts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2014

Microscopic Theory of the Long-Time Diffusivity and Intermediate-Time Anomalous Transport of a Nanoparticle in Polymer Melts

The transport of a single nanoparticle in unentangled and entangled polymer melts is studied based on a microscopic, force-level, self-consistent generalized Langevin equation approach. Nanoparticle self-motion and length-scale-dependent polymer relaxation enter as two parallel and competing channels of force relaxation. For entangled melts, particle long-time mobility exhibits size-dependent non-Stokes–Einstein behaviors controlled by (i) fast diffusion and length-scale-dependent collective relaxation of the unentangled matrix for particles smaller than the tube diameter and (ii) polymer relaxation via reptation for nanoparticles larger than the tube diameter. The two regimes are connected by a relatively sharp but continuous crossover. Recovery of hydrodynamic behavior requires the nanoparticle to be roughly 10 times larger than the tube diameter. Theoretical predictions for the diffusion constant are in good agreement with recent simulations of unentangled and lightly entangled melts, including the crossover regime where the nanoparticle and tube diameters are roughly equal. The calculations are also in reasonable accord with several experiments in entangled synthetic polymer melts and DNA solutions, although the activated hopping motion not included in the present theory may be important in a narrow intermediate crossover regime for sufficiently entangled polymers. The predictions of the theory for intermediate-time anomalous diffusion are of mixed quality based on comparison to simulations. Furthermore, the significant limitations identified are associated with our minimalist treatment of collective density fluctuation relaxation on intermediate time and length scales, including the possible importance of non-reptation relaxation processes in entangled melts.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

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