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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Reference interaction site model with hydrophobicity induced density inhomogeneity: An analytical theory to compute solvation properties of large hydrophobic solutes in the mixture of polyatomic solvent molecules

Reference interaction site model (RISM) has recently become a popular approach in the study of thermodynamical and structural properties of the solvent around macromolecules. On the other hand, it was widely suggested that there exists water density depletion around large hydrophobic solutes (>1 nm), and this may pose a great challenge to the RISM theory. In this paper, we develop a new analytical theory, the Reference Interaction Site Model with Hydrophobicity induced density Inhomogeneity (RISM-HI), to compute solvent radial distribution function (RDF) around large hydrophobic solute in water as well as its mixture with other polyatomic organic solvents. To achieve this, we have explicitly considered the density inhomogeneity at the solute-solvent interface using the framework of the Yvon-Born-Green hierarchy, and the RISM theory is used to obtain the solute-solvent pair correlation. In order to efficiently solve the relevant equations while maintaining reasonable accuracy, we have also developed a new closure called the D2 closure. With this new theory, the solvent RDFs around a large hydrophobic particle in water and different water-acetonitrile mixtures could be computed, which agree well with the results of the molecular dynamics simulations. Furthermore, we show that our RISM-HI theory can also efficiently compute the solvation free energy of solute with a wide range of hydrophobicity in various water-acetonitrile solvent mixtures with a reasonable accuracy. We anticipate that our theory could be widely applied to compute the thermodynamic and structural properties for the solvation of hydrophobic solute.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Density of hydrophobically confined deeply cooled water investigated by small angle X-ray scattering

Water’s behavior near hydrophobic surfaces has attracted great attention due to chemical and geological applications. Here, we report small angle X-ray scattering (SAXS) studies of water confined in the hydrophobic nanoporous carbon material, CMK-1-14, from ambient to deeply cooled temperatures. By monitoring the scattering intensity of the first Bragg peak, which is directly related to the scattering length density contrast between the carbon matrix and the confined water, the average density of the hydrophobically confined water was determined from 300 K to 150 K at ambient pressure. Furthermore, differential scanning calorimetry and X-ray diffraction measurements showed that the majority of such hydrophobically confined water did not crystallize in the investigated temperature range. By exploiting the fast speed of SAXS measurements and the continuous temperature ramping, the average density profile and the deduced thermal expansion coefficient (α{sub p}) were obtained. We found that the well-known density maximum of water at 277 K downshifted to 260 K, and the density minimum which has been observed in hydrophilic confinement disappeared. In addition, the previously measured large density decreasing of 18% at low temperature was recalibrated to a more reasonable 10% instead. Consequently, the recalculated α{sub p} peak was found to be quite similar to that of the water confined in hydrophilic MCM-41-S-15 suggesting an intrinsic property of water, which does not sensitively depend on the confinement surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Jet formation in cerium metal to examine material strength

Examining the evolution of material properties at extreme conditions advances our understanding of numerous high-pressure phenomena from natural events like meteorite impacts to general solid mechanics and fluid flow behavior. Recent advances in synchrotron diagnostics coupled with dynamic compression platforms have introduced new possibilities for examining in-situ, spatially resolved material response with nanosecond time resolution. In this work, we examined jet formation from a Richtmyer-Meshkov instability in cerium initially shocked into a transient, high-pressure phase, and then released to a low-pressure, higher-temperature state. Cerium's rich phase diagram allows us to study the yield stress following a shock induced solid-solid phase transition. X-ray imaging was used to obtain images of jet formation and evolution with 2–3 μm spatial resolution. From these images, an analytic method was used to estimate the post-shock yield stress, and these results were compared to continuum calculations that incorporated an experimentally validated equation-of-state (EOS) for cerium coupled with a deviatoric strength model. Reasonable agreement was observed between the calculations and the data illustrating the sensitivity of jet formation on the yield stress values. The data and analysis shown here provide insight into material strength during dynamic loading which is expected to aid in the development of strength aware multi-phase EOS required to predict the response of matter at extreme conditions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Design of indirectly driven, high-compression Inertial Confinement Fusion implosions with improved hydrodynamic stability using a 4-shock adiabat-shaped drive

Experimental results from indirectly driven ignition implosions during the National Ignition Campaign (NIC) [M. J. Edwards et al., Phys. Plasmas 20, 070501 (2013)] achieved a record compression of the central deuterium-tritium fuel layer with measured areal densities up to 1.2 g/cm{sup 2}, but with significantly lower total neutron yields (between 1.5 × 10{sup 14} and 5.5 × 10{sup 14}) than predicted, approximately 10% of the 2D simulated yield. An order of magnitude improvement in the neutron yield was subsequently obtained in the “high-foot” experiments [O. A. Hurricane et al., Nature 506, 343 (2014)]. However, this yield was obtained at the expense of fuel compression due to deliberately higher fuel adiabat. In this paper, the design of an adiabat-shaped implosion is presented, in which the laser pulse is tailored to achieve similar resistance to ablation-front instability growth, but with a low fuel adiabat to achieve high compression. Comparison with measured performance shows a factor of 3–10× improvement in the neutron yield (>40% of predicted simulated yield) over similar NIC implosions, while maintaining a reasonable fuel compression of >1 g/cm{sup 2}. Extension of these designs to higher laser power and energy is discussed to further explore the trade-off between increased implosion velocity and the deleterious effects of hydrodynamic instabilities.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Alternative modeling methods for plasma-based Rf ion sources

Rf-driven ion sources for accelerators and many industrial applications benefit from detailed numerical modeling and simulation of plasma characteristics. For instance, modeling of the Spallation Neutron Source (SNS) internal antenna H{sup −} source has indicated that a large plasma velocity is induced near bends in the antenna where structural failures are often observed. This could lead to improved designs and ion source performance based on simulation and modeling. However, there are significant separations of time and spatial scales inherent to Rf-driven plasma ion sources, which makes it difficult to model ion sources with explicit, kinetic Particle-In-Cell (PIC) simulation codes. In particular, if both electron and ion motions are to be explicitly modeled, then the simulation time step must be very small, and total simulation times must be large enough to capture the evolution of the plasma ions, as well as extending over many Rf periods. Additional physics processes such as plasma chemistry and surface effects such as secondary electron emission increase the computational requirements in such a way that even fully parallel explicit PIC models cannot be used. One alternative method is to develop fluid-based codes coupled with electromagnetics in order to model ion sources. Time-domain fluid models can simulate plasma evolution, plasma chemistry, and surface physics models with reasonable computational resources by not explicitly resolving electron motions, which thereby leads to an increase in the time step. This is achieved by solving fluid motions coupled with electromagnetics using reduced-physics models, such as single-temperature magnetohydrodynamics (MHD), extended, gas dynamic, and Hall MHD, and two-fluid MHD models. We show recent results on modeling the internal antenna H{sup −} ion source for the SNS at Oak Ridge National Laboratory using the fluid plasma modeling code USim. We compare demonstrate plasma temperature equilibration in two-temperature MHD models for the SNS source and present simulation results demonstrating plasma evolution over many Rf periods for different plasma temperatures. We perform the calculations in parallel, on unstructured meshes, using finite-volume solvers in order to obtain results in reasonable time.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2015

Coarse-grained simulations of polyelectrolyte complexes: MARTINI models for poly(styrene sulfonate) and poly(diallyldimethylammonium)

We present simulations of aqueous polyelectrolyte complexes with new MARTINI models for the charged polymers poly(styrene sulfonate) and poly(diallyldimethylammonium). Our coarse-grained polyelectrolyte models allow us to study large length and long time scales with regard to chemical details and thermodynamic properties. The results are compared to the outcomes of previous atomistic molecular dynamics simulations and verify that electrostatic properties are reproduced by our MARTINI coarse-grained approach with reasonable accuracy. Structural similarity between the atomistic and the coarse-grained results is indicated by a comparison between the pair radial distribution functions and the cumulative number of surrounding particles. Our coarse-grained models are able to quantitatively reproduce previous findings like the correct charge compensation mechanism and a reduced dielectric constant of water. These results can be interpreted as the underlying reason for the stability of polyelectrolyte multilayers and complexes and validate the robustness of the proposed models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Simulations of the THz spectrum of liquid water incorporating the effects of intermolecular charge fluxes through hydrogen bonds

The intensity of the band at ∼200 cm{sup −1} (∼6 THz) in the Terahertz spectrum of liquid water mainly arises from the modulations of the extent of intermolecular charge transfer through hydrogen bonds, called intermolecular charge fluxes, occurring upon molecular translations along the O…H hydrogen bonds. To obtain reasonable spectral profiles from simulations, it is necessary to effectively incorporate the effects of those intermolecular charge fluxes, but apparently it is not possible by simple classical molecular dynamics simulations with fixed atomic partial charges even if they are amended by molecular induced dipoles due to intermolecular electrostatic interactions. The present paper shows how we can do reasonably correct spectral simulations, without resorting to fully ab initio molecular dynamics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Vapor shielding models and the energy absorbed by divertor targets during transient events

The erosion of divertor targets caused by high heat fluxes during transients is a serious threat to ITER operation, as it is going to be the main factor determining the divertor lifetime. Under the influence of extreme heat fluxes, the surface temperature of plasma facing components can reach some certain threshold, leading to an onset of intense material evaporation. The latter results in formation of cold dense vapor and secondary plasma cloud. This layer effectively absorbs the energy of the incident plasma flow, turning it into its own kinetic and internal energy and radiating it. This so called vapor shielding is a phenomenon that may help mitigating the erosion during transient events. In particular, the vapor shielding results in saturation of energy (per unit surface area) accumulated by the target during single pulse of heat load at some level E{sub max}. Matching this value is one of the possible tests to verify complicated numerical codes, developed to calculate the erosion rate during abnormal events in tokamaks. The paper presents three very different models of vapor shielding, demonstrating that E{sub max} depends strongly on the heat pulse duration, thermodynamic properties, and evaporation energy of the irradiated target material. While its dependence on the other shielding details such as radiation capabilities of material and dynamics of the vapor cloud is logarithmically weak. The reason for this is a strong (exponential) dependence of the target material evaporation rate, and therefore the “strength” of vapor shield on the target surface temperature. As a result, the influence of the vapor shielding phenomena details, such as radiation transport in the vapor cloud and evaporated material dynamics, on the E{sub max} is virtually completely masked by the strong dependence of the evaporation rate on the target surface temperature. However, the very same details define the amount of evaporated particles, needed to provide an effective shielding to the target, and, therefore, strongly influence resulting erosion rate. Thus, E{sub max} cannot be used for validation of shielding models and codes, aimed at the target material erosion calculations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Oscillatory reaction cross sections caused by normal mode sampling in quasiclassical trajectory calculations

The quasiclassical trajectory (QCT) method is an efficient and important tool for studying the dynamics of bimolecular reactions. In this method, the motion of the atoms is simulated classically, and the only quantum effect considered is that the initial vibrational states of reactant molecules are semiclassically quantized. A sensible expectation is that the initial ensemble of classical molecular states generated this way should be stationary, similarly to the quantum state it is supposed to represent. The most widely used method for sampling the vibrational phase space of polyatomic molecules is based on the normal mode approximation. In the present work, it is demonstrated that normal mode sampling provides a nonstationary ensemble even for a simple molecule like methane, because real potential energy surfaces are anharmonic in the reactant domain. The consequences were investigated for reaction CH{sub 4} + H → CH{sub 3} + H{sub 2} and its various isotopologs and were found to be dramatic. Reaction probabilities and cross sections obtained from QCT calculations oscillate periodically as a function of the initial distance of the colliding partners and the excitation functions are erratic. The reason is that in the nonstationary ensemble of initial states, the mean bond length of the breaking C–H bond oscillates in time with the frequency of the symmetric stretch mode. We propose a simple method, one-period averaging, in which reactivity parameters are calculated by averaging over an entire period of the mean C–H bond length oscillation, which removes the observed artifacts and provides the physically most reasonable reaction probabilities and cross sections when the initial conditions for QCT calculations are generated by normal mode sampling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say “the most important emerging energy technology” is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is still the main problem on developing the lithium ion battery.The safety issue must be considered from several aspects, since it would become serious problems, such as an explosion in a Japan Airlines 787 Dreamliner’s cargo hold, due to the battery problem. The combustion is mainly due to the leakage or shortcut of the electrodes, caused by the liquid electrolyte and polymer separator. For this reason, the research on solid electrolyte for replacing the existing liquid electrolyte is very important. The materials used in existing lithium ion battery, such as a separator and liquid electrolyte must be replaced to new solid electrolytes, solid materials that exhibits high ionic conductivity. Due to these reasons, research on solid state ionics materials have been vastly growing worldwide, with the main aim not only to search new solid electrolyte to replace the liquid one, but also looking for low cost materials and environmentally friendly. A revolutionary paradigm is also required to design new stable anode and cathode materials that provide electrochemical cells with high energy, high power, long lifetime and adequate safety at competitive manufacturing costs. Lithium superionic conductors, which can be used as solid electrolytes, promise the potential to replace organic liquid electrolytes and thereby improve the safety of next-generation high-energy batteries. Li{sub 3}PO{sub 4} has been proved to be a good candidate for solid electrolyte, due to its easy in preparation, low cost, high melting temperature and good compatibility with the electrode materials. In the present work, Li{sub 3}PO{sub 4} has been prepared by wet chemical reaction, a simple method with the advantage of recycling a waste product H{sub 3}PO{sub 4}. The crystal structure has been characterized by both neutron and x-ray diffraction. The use of neutron scattering plays important role on observing the light atoms such as lithium ion. The x-ray diffraction results showed the crystal structure of orthorhombic phase P m n 21 (31), that belongs to the β-Li{sub 3}PO{sub 4}, with the lattice parameters are a = 6.123872, b = 5.250211, c = 4.876378. The conductivity of β-Li{sub 3}PO{sub 4} was around 10{sup −8} S/cm. Furthermore, the future application of the solid electrolyte layer in lithium ion battery will also be considered. It is concluded that the used of local resources on producing the solid electrolyte Li{sub 3}PO{sub 4} for lithium ion battery will give more added values to the researches and national industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Three-dimensional simulations of low foot and high foot implosion experiments on the National Ignition Facility

In order to achieve the several hundred Gbar stagnation pressures necessary for inertial confinement fusion ignition, implosion experiments on the National Ignition Facility (NIF) [E. I. Moses et al., Phys. Plasmas 16, 041006 (2009)] require the compression of deuterium-tritium fuel layers by a convergence ratio as high as forty. Such high convergence implosions are subject to degradation by a range of perturbations, including the growth of small-scale defects due to hydrodynamic instabilities, as well as longer scale modulations due to radiation flux asymmetries in the enclosing hohlraum. Due to the broad range of scales involved, and also the genuinely three-dimensional (3D) character of the flow, accurately modeling NIF implosions remains at the edge of current simulation capabilities. This paper describes the current state of progress of 3D capsule-only simulations of NIF implosions aimed at accurately describing the performance of specific NIF experiments. Current simulations include the effects of hohlraum radiation asymmetries, capsule surface defects, the capsule support tent and fill tube, and use a grid resolution shown to be converged in companion two-dimensional simulations. The results of detailed simulations of low foot implosions from the National Ignition Campaign are contrasted against results for more recent high foot implosions. While the simulations suggest that low foot performance was dominated by ablation front instability growth, especially the defect seeded by the capsule support tent, high foot implosions appear to be dominated by hohlraum flux asymmetries, although the support tent still plays a significant role. For both implosion types, the simulations show reasonable, though not perfect, agreement with the data and suggest that a reliable predictive capability is developing to guide future implosions toward ignition.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Enhancement of thermoelectric properties by energy filtering: Theoretical potential and experimental reality in nanostructured ZnSb

Energy filtering has been suggested by many authors as a means to improve thermoelectric properties. The idea is to filter away low-energy charge carriers in order to increase Seebeck coefficient without compromising electronic conductivity. This concept was investigated in the present paper for a specific material (ZnSb) by a combination of first-principles atomic-scale calculations, Boltzmann transport theory, and experimental studies of the same system. The potential of filtering in this material was first quantified, and it was as an example found that the power factor could be enhanced by an order of magnitude when the filter barrier height was 0.5 eV. Measured values of the Hall carrier concentration in bulk ZnSb were then used to calibrate the transport calculations, and nanostructured ZnSb with average grain size around 70 nm was processed to achieve filtering as suggested previously in the literature. Various scattering mechanisms were employed in the transport calculations and compared with the measured transport properties in nanostructured ZnSb as a function of temperature. Reasonable correspondence between theory and experiment could be achieved when a combination of constant lifetime scattering and energy filtering with a 0.25 eV barrier was employed. However, the difference between bulk and nanostructured samples was not sufficient to justify the introduction of an energy filtering mechanism. The reasons for this and possibilities to achieve filtering were discussed in the paper.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

On the inward drift of runaway electrons during the plateau phase of runaway current

The well observed inward drift of current carrying runaway electrons during runaway plateau phase after disruption is studied by considering the phase space dynamic of runaways in a large aspect ratio toroidal system. We consider the case where the toroidal field is unperturbed and the toroidal symmetry of the system is preserved. The balance between the change in canonical angular momentum and the input of mechanical angular momentum in such a system requires runaways to drift horizontally in configuration space for any given change in momentum space. The dynamic of this drift can be obtained by integrating the modified Euler-Lagrange equation over one bounce time. It is then found that runaway electrons will always drift inward as long as they are decelerating. This drift motion is essentially non-linear, since the current is carried by runaways themselves, and any runaway drift relative to the magnetic axis will cause further displacement of the axis itself. A simplified analytical model is constructed to describe such inward drift both in the ideal wall case and no wall case, and the runaway current center displacement as a function of parallel momentum variation is obtained. The time scale of such displacement is estimated by considering effective radiation drag, which shows reasonable agreement with the observed displacement time scale. Furthermore, this indicates that the phase space dynamic studied here plays a major role in the horizontal displacement of runaway electrons during plateau phase. (C) 2016 AIP Publishing LLC.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Synthesis of a mixed-valent tin nitride and considerations of its possible crystal structures

Recent advances in theoretical structure prediction methods and high-throughput computational techniques are revolutionizing experimental discovery of the thermodynamically stable inorganic materials. Metastable materials represent a new frontier for these studies, since even simple binary non-ground state compounds of common elements may be awaiting discovery. However, there are significant research challenges related to non-equilibrium thin film synthesis and crystal structure predictions, such as small strained crystals in the experimental samples and energy minimization based theoretical algorithms. Here, we report on experimental synthesis and characterization, as well as theoretical first-principles calculations of a previously unreported mixed-valent binary tin nitride. Thin film experiments indicate that this novel material is N-deficient SnN with tin in the mixed II/IV valence state and a small low-symmetry unit cell. Theoretical calculations suggest that the most likely crystal structure has the space group 2 (SG2) related to the distorted delafossite (SG166), which is nearly 0.1 eV/atom above the ground state SnN polymorph. This observation is rationalized by the structural similarity of the SnN distorted delafossite to the chemically related Sn{sub 3}N{sub 4} spinel compound, which provides a fresh scientific insight into the reasons for growth of polymorphs of metastable materials. In addition to reporting on the discovery of the simple binary SnN compound, this paper illustrates a possible way of combining a wide range of advanced characterization techniques with the first-principle property calculation methods, to elucidate the most likely crystal structure of the previously unreported metastable materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

On the applicability of one- and many-electron quantum chemistry models for hydrated electron clusters

We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions with n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Dynamics of ion beam charge neutralization by ferroelectric plasma sources

Ferroelectric Plasma Sources (FEPSs) can generate plasma that provides effective space-charge neutralization of intense high-perveance ion beams, as has been demonstrated on the Neutralized Drift Compression Experiment NDCX-I and NDCX-II. This article presents experimental results on charge neutralization of a high-perveance 38 keV Ar + beam by a plasma produced in a FEPS discharge. By comparing the measured beam radius with the envelope model for space-charge expansion, it is shown that a charge neutralization fraction of 98% is attainable with sufficiently dense FEPS plasma. The transverse electrostatic potential of the ion beam is reduced from 15V before neutralization to 0.3 V, implying that the energy of the neutralizing electrons is below 0.3 eV. Measurements of the time-evolution of beam radius show that near-complete charge neutralization is established similar to –5 μs after the driving pulse is applied to the FEPS and can last for 35 μs. It is argued that the duration of neutralization is much longer than a reasonable lifetime of the plasma produced in the sub-mu s surface discharge. Measurements of current flow in the driving circuit of the FEPS show the existence of electron emission into vacuum, which lasts for tens of mu s after the high voltage pulse is applied. Lastly, it is argued that the beam is neutralized by the plasma produced by this process and not by a surface discharge plasma that is produced at the instant the high-voltage pulse is applied.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH{sub 4} on Pt(111)

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH{sub 4} dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v{sub 3} and 2v{sub 3}, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v{sub 1} symmetric stretch of CH{sub 4} is more effective at promoting the dissociative chemisorption of CH{sub 4} than exciting the 1v{sub 3} antisymmetric stretch. This behavior is explained in terms of symmetry, mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v{sub 3} state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. Our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Anharmonic densities of states: A general dynamics-based solution

Density of states is a fundamental physical characteristic that lies at the foundation of statistical mechanics and theoretical constructs that derive from them (e.g., kinetic rate theories, phase diagrams, and others). Even though most real physical systems are anharmonic, the vibrational density of states is customarily treated within the harmonic approximation, or with some partial, often limited, account for anharmonicity. The reason for this is that the problem of anharmonic densities of states stubbornly resisted a general and exact, yet convenient and straightforward in applications, solution. Here we formulate such a solution within both classical and quantum mechanics. It is based on actual dynamical behavior of systems as a function of energy and as observed, or monitored, on a chosen time scale, short or long. As a consequence, the resulting anharmonic densities of states are fully dynamically informed and, in general, time-dependent. As such, they lay the ground for formulation of new statistical mechanical frameworks that incorporate time and are ergodic, by construction, with respect to actual dynamical behavior of systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗