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At least 685 records · Page 38

Rates of oxidative weathering on the surface of Mars

Implicit in the mnemonic 'MSATT' (Mars surface and atmosphere through time) is that rates of surface processes on Mars through time should be investigated, including studies of the kinetics and mechanism of oxidative weathering reactions occurring in the Martian regolith. Such measurements are described. Two major elements analyzed in the Viking Lander XRF experiment that are most vulnerable to atmospheric oxidation are iron and sulfur. Originally, they occurred as Fe(2+)-bearing silicate and sulfide minerals in basaltic rocks on the surface of Mars. However, chemical weathering reactions through time have produced ferric- and sulfate-bearing assemblages now visible in the Martian regolith. Such observations raise several question about: (1) when the oxidative weathering reactions took place on Mars; (2) whether or not the oxidized regolith is a fossilized remnant of past weathering processes; (3) deducting chemical interactions of the ancient Martian atmosphere with its surface from surviving phases; (4) possible weathering reactions still occurring in the frozen regolith; and (5) the kinetics and mechanism of past and present-day oxidative reactions on Mars. These questions may be addressed experimentally by studying reaction rates of dissolution and oxidation of basaltic minerals, and by identifying reaction products forming on the mineral surfaces. Results for the oxidation of pyrrhotite and dissolved ferrous iron are reported.

Burns, Roger G.↗

Laser-Induced Fluorescence Measurements and Modeling of Nitric Oxide in Counterflow Diffusion Flames

The feasibility of making quantitative nonintrusive NO concentration ([NO]) measurements in nonpremixed flames has been assessed by obtaining laser-induced fluorescence (LIF) measurements of [NO] in counterflow diffusion flames at atmospheric and higher pressures. Comparisons at atmospheric pressure between laser-saturated fluorescence (LSF) and linear LIF measurements in four diluted ethane-air counterflow diffusion flames with strain rates from 5 to 48/s yielded excellent agreement from fuel-lean to moderately fuel-rich conditions, thus indicating the utility of a model-based quenching correction technique, which was then extended to higher pressures. Quantitative LIF measurements of [NO] in three diluted methane-air counterflow diffusion flames with strain rates from 5 to 35/s were compared with OPPDIF model predictions using the GRI (version 2.11) chemical kinetic mechanism. The comparisons revealed that the GRI mechanism underpredicts prompt-NO by 30-50% at atmospheric pressure. Based on these measurements, a modified reaction rate coefficient for the prompt-NO initiation reaction was proposed which causes the predictions to match experimental data. Temperature measurements using thin filament pyrometry (TFP) in conjunction with a new calibration method utilizing a near-adiabatic H2-air Hencken burner gave very good comparisons with model predictions in these counterflow diffusion flames. Quantitative LIF measurements of [NO] were also obtained in four methane-air counterflow partially-premixed flames with fuel-side equivalence ratios (phi(sub B)) of 1.45, 1.6, 1.8 and 2.0. The measurements were in excellent agreement with model predictions when accounting for radiative heat loss. Spatial separation between regions dominated by the prompt and thermal NO mechanisms was observed in the phi(sub B) = 1.45 flame. The modified rate coefficient proposed earlier for the prompt-NO initiation reaction improved agreement between code predictions and measurements in the region where prompt-NO dominates. Finally, LIF measurements of NO were obtained in counterflow diffusion flames at 2 to 5 atm. Comparisons between [NO] measurements and predictions show that the GRI mechanism underpredicts prompt-NO by a factor of two to three at all pressures. In general, the results indicate a need for refinement of the CH chemistry, especially the pressure-dependent CH formation and destruction reactions.

Ravikrishna, Rayavarapu V.↗

Comparison of PDF and Moment Closure Methods in the Modeling of Turbulent Reacting Flows

In modeling turbulent reactive flows, Probability Density Function (PDF) methods have an advantage over the more traditional moment closure schemes in that the PDF formulation treats the chemical reaction source terms exactly, while moment closure methods are required to model the mean reaction rate. The common model used is the laminar chemistry approximation, where the effects of turbulence on the reaction are assumed negligible. For flows with low turbulence levels and fast chemistry, the difference between the two methods can be expected to be small. However for flows with finite rate chemistry and high turbulence levels, significant errors can be expected in the moment closure method. In this paper, the ability of the PDF method and the moment closure scheme to accurately model a turbulent reacting flow is tested. To accomplish this, both schemes were used to model a CO/H2/N2- air piloted diffusion flame near extinction. Identical thermochemistry, turbulence models, initial conditions and boundary conditions are employed to ensure a consistent comparison can be made. The results of the two methods are compared to experimental data as well as to each other. The comparison reveals that the PDF method provides good agreement with the experimental data, while the moment closure scheme incorrectly shows a broad, laminar-like flame structure.

Norris, Andrew T.↗

Reactive Transport Modeling of Anthropogenic Carbon Mineralization in Stacked Columbia River Basalt Reservoirs

Numerical simulation of CO2 storage in basalts and related reactive lithologies requires modeling complex, coupled hydrologic and chemical processes, including multi-phase flow and transport, partitioning of CO2 into the aqueous phase, and chemical interactions with aqueous fluids and rock minerals. We conducted reactive transport simulations of the Wallula pilot-scale CO2 injection into the flow tops of the Grande Ronde Basalt using our PNNL STOMP-CO2 simulator with the ECKEChem reactive module. Our mineralization simulation of the ~1,000 tons of injected CO2 into the interflow zones was based on the hydrologic transport model we previously developed. For this work, the simulations considered geochemical reactions involving the basalt components, precipitates, formation brine, and injected CO2. In our benchmark case, carbonate minerals precipitated, resulting in ~20% of the CO2 being mineralized in 10 years. Increasing the reaction rate of a single primary mineral phase (clinopyroxene) by an order of magnitude resulted in a carbon mineralization reaction extent of ~90% over the same time interval. Based on these initial sensitivity analysis results, it is clear that a thorough understanding of primary mineral dissolution rates is required for accurately predicting long-term fate and transport of injected CO2 into basalt formations. Our reactive transport numerical simulations will be key components of commercial-scale CO2 storage operation permitting, de-risking, and optimization in mafic and ultramafic reservoirs.

Cao, Ruoshi↗

Estimating the Backup Reaction Wheel Orientation Using Reaction Wheel Spin Rates Flight Telemetry from a Spacecraft

A report describes a model that estimates the orientation of the backup reaction wheel using the reaction wheel spin rates telemetry from a spacecraft. Attitude control via the reaction wheel assembly (RWA) onboard a spacecraft uses three reaction wheels (one wheel per axis) and a backup to accommodate any wheel degradation throughout the course of the mission. The spacecraft dynamics prediction depends upon the correct knowledge of the reaction wheel orientations. Thus, it is vital to determine the actual orientation of the reaction wheels such that the correct spacecraft dynamics can be predicted. The conservation of angular momentum is used to estimate the orientation of the backup reaction wheel from the prime and backup reaction wheel spin rates data. The method is applied in estimating the orientation of the backup wheel onboard the Cassini spacecraft. The flight telemetry from the March 2011 prime and backup RWA swap activity on Cassini is used to obtain the best estimate for the backup reaction wheel orientation.

Rizvi, Farheen↗

Absolute rate of the reaction of Cl/2P/ with methane from 200-500 K

Rate constants for the reaction Cl + CH4 yields HCl + CH3 were measured in the range 200-500 K by the plot flash photolysis-resonance fluorescence technique. An Arrhenius plot of the mean rate constant observed at 14 equally spaced temperatures is best fit by the expression k = 5.44 times 10 to the minus 19th times T to the exponent 2.50 times exp(-608/T) cu cm per molecule per sec. Appropriate expressions are also given for the rate constant in the two ranges 200-299 K and 299-500 K. These results are compared with a number of other existing determinations of the rate constant by other methods and in different temperature ranges. Most discrepancies are attributed to the nonlinear Arrhenius behavior.

Whytock, D. A.↗

Hydrothermal corrosion behavior of CVD SiC in high temperature water

Here, the hydrothermal corrosion of polished and as-cut high purity chemical vapor deposited (CVD) SiC was studied in a constantly refreshing water loop. Light water reactor (LWR) conditions were simulated at 288, 320, and 350 °C with dissolved gas concentrations between 0.15 and 3 ppm H 2 or between 1 and 4 ppm O 2 . In hydrogenated water, the rate of material loss was low, calculated to be ~1.3 μm of recession after 5 years of service in 320 °C water. Moreover, there was no observed localized attack at any temperature. In oxygenated conditions, the corrosion rate was higher, with a calculated material loss >10 μm after 5 years of service in 1 ppm O 2 , 320 °C water. Mass loss significantly increased when grain fallout became significant (as early as 200h with 4 ppm O 2 at 350 °C or after 1000–2000h with 2 ppm O 2 at 288 °C). Grain fallout more than doubled the corrosion rate and a steady state corrosion rate in the grain fallout regime was not observed but expected to eventually occur once large grains begin to be removed. Polished specimens had lower mass loss than unpolished coupons. A kinetic analysis of the data in this work suggests that the corrosion rates are controlled by a single activation step in both oxygenated and deoxygenated conditions, with the reaction order with respect to oxygen being 1. A resulting reaction rate equation to predict corrosion of SiC (in mg/cm 2 s) in high purity water from 288 to 350 °C and up to 4 ppm O 2 was constructed: Rate = $\frac{0.1458}{1+SA}$ T (1.09(1–10 -3 T)[O 2 ]e– $\frac{1.275x10^4}{T}$ + 7.91x10 -6 e– $\frac{7.39x10^3}{T}$).

36 MATERIALS SCIENCE↗

Fission and the r -process nucleosynthesis of translead nuclei in neutron star mergers

In this report we study the impact of fission on the production and destruction of translead nuclei during the r-process nucleosynthesis occurring in neutron-star mergers. Abundance patterns and rates of nuclear energy production are obtained for different ejecta conditions using three sets of stellar reaction rates, one of which is based on microscopic and consistent calculations of nuclear masses, fission barriers, and collective inertias. We show that the accumulation of fissioning material during the r process can strongly affect the free neutron abundance after the r-process freeze-out. This leads to a significant impact on the abundances of heavy nuclei that undergo α decay or spontaneous fission, affecting the radioactive energy production by the ejecta at timescales relevant for kilonova emission.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Neutron radiation characteristics of plutonium dioxide fuel

The major sources of neutrons from plutonium dioxide nuclear fuel are considered in detail. These sources include spontaneous fission of several of the Pu isotopes, (alpha, n) reactions with low Z impurities in the fuel, and (alpha, n) reactions with O-18. For spontaneous fission neutrons a value of (1.95 + or - 0.07) X 1,000 n/s/g PuO2 is obtained. The neutron yield from (alpha, n) reactions with oxygen is calculated by integrating the reaction rate equation over all alpha-particle energies and all center-of-mass angles. The results indicate a neutron emission rate of (1.14 + or - 0.26) X 10,000 n/s/g PuO2. The neutron yield from (alpha, n) reactions with low Z impurities in the fuel is presented in tabular form for one part part per million of each impurity. The total neutron yield due to the combined effects of all the impurities depends upon the fractional weight concentration of each impurity. The total neutron flux emitted from a particular fuel geometry is estimated by adding the neutron yield due to the induced fission to the other neutron sources.

Taherzadeh, M.↗

Strain-Rate-Free Diffusion Flames: Initiation, Properties, and Quenching

For about a half century, the stabilization of a steady planar deflagration on a heat-sink-type flat-flame burner has been of extraordinary service for the theoretical modeling and diagnostic probing of combusting gaseous mixtures. However, most engineering devices and most unwanted fire involve the burning of initially unmixed reactants. The most vigorous burning of initially separated gaseous fuel and oxidizer is the diffusion flame. In this useful idealization (limiting case), the reactants are converted to product at a mathematically thin interface, so no interpenetration of fuel and oxidizer occurs. This limit is of practical importance because it often characterizes the condition of optimal performance (and sometimes environmentally objectionable operation) of a combustor. A steady planar diffusion flame is most closely approached in the laboratory in the counterflow apparatus. The utility of this simple-strain-rate flow for the modeling and probing of diffusion flames was noted by Pandya and Weinberg 35 years ago, though only in the last decade or so has its use become internationally common place. However, typically, as the strain rate a is reduced below about 20 cm(exp -1), and the diffusion-flame limit (reaction rate much faster than the flow rate) is approached, the burning is observed to become unstable in earth gravity. The advantageous steady planar flow is not available in the diffusion-flame limit in earth gravity. This is unfortunate because the typical spatial scale in a counterflow is (k/a)(sup 1/2), where k denotes a characteristic diffusion coefficient; thus, the length scale becomes large, and the reacting flow is particularly amenable to diagnostic probing, as the diffusion-flame limit is approached. The disruption of planar symmetry is owing the fact that, as the strain rate a decreases, the residence time (l/a) of the throughput in the counterflow burner increases. Observationally, when the residence time exceeds about 50 msec, the inevitably present convective (Rayleigh-Benard) instabilities, associated with hot-under-cold (flame-under-fresh-reactant) stratification of fluid in a gravitational field, have time to grow to finite amplitude during transit of the burner.

Fendell, Francis↗

A new way to unravel the $^{12}$C($\alpha $,$\gamma $)$^{16}$O cross section components using neural networks

The $^{12}$C($\alpha $,$\gamma $)$^{16}$O reaction rate is crucial in determining the carbon-to-oxygen abundance ratio in stellar nucleosynthesis. Measuring this reaction’s cross section at stellar energies is challenging due to its extremely small value, approximately 10 -17 barn at E c.m. = 300 keV. To address this, R-matrix calculations are employed to extrapolate data to lower energies, requiring a comprehensive understanding of each contribution to the cross section. The dominant contributions to the cross section at stellar energies arise from electric dipole (E1) and electric quadrupole (E2) transitions to the ground state of 16 O, along with a significant cascade contribution. Traditionally, these contributions have been separated using the γ-ray angular distribution. In this work, we propose a novel technique using the energy distribution of the 16 O recoils at the focal plane. This method involves a neural network trained on detailed Monte Carlo simulations of the energy distribution of recoils transported through the recoil mass separator ERNA. This approach enables the simultaneous determination of all three contributions with errors around 10% in the energy range E c.m. = 1.0–2.2 MeV. In conclusion, by employing this new technique, we aim to significantly improve the accuracy of determining the cross section of the $^{12}$C($\alpha $,$\gamma $)$^{16}$O reaction at astrophysical energies.

Astrochemistry↗

Dislocation Patterning in Deforming Crystals: Theory, Computational Predictions and Validation (Final Technical Report)

This project was awarded for an initial period of three years, followed by a no-cost extension for one year and a funded one-year renewal. During the first four years, the project focused on investigating the role of dislocation reactions and dislocation correlation in dislocation patterning in FCC metals. During the fifth year, the scope of research was expanded to investigate the effects of composition inhomogeneity on the mesoscale plastic response of Body-Centered Cubic (BCC) alloys. In addition to its impact on metal hardening during deformation, dislocation patterning provides the microstructure information required to understand phenomena like fracture and recrystallization in metals. The Continuum Dislocation Dynamics (CDD) framework was the methodology used during the first four years, followed by the use of Discrete Dislocation Dynamics (DDD) during the fifth year. CDD is a density-based formalism of dislocation dynamics in which the plastic deformation of crystals is predicted together with the mesoscale dislocation patterns by tracking the space-time evolution of dislocations as driven by the applied stress, short-range and long-range interactions of dislocations, and cross slip. CDD is a crystal mechanics approach in which the plastic constitutive part is replaced with the equations of dislocation dynamics, which is driven by the internal stress via a mobility laws, while the evolution of the density gives the eigenstrain required to update the internal stress itself. The governing equations are thus those of crystal mechanics cast as an eigenstrain problem and those of dislocation transport and reactions. Our investigations during the first four years were driven by the hypothesis that that dislocation patterning is triggered by spatiotemporal dislocation density and internal stress fluctuations, and that such fluctuations influence the collective dislocation dynamic through their effects on the short-range reaction rates and the collective dislocation mobility. This hypothesis was tested by modeling the influence of the dislocation reactions and dislocation correlations on collective dislocation dynamics. The main research components during the first four years were: 1) Reformulation of the CDD framework to integrate the dislocation correlations and dislocation reactions. 2) Simulation of the dislocation correlations and quantifying their contribution to the long-range stress of complex dislocation systems. 3) Computational implementation of the updated CDD model for FCC single crystals and development of an efficient CDD code. 4) Investigation of dislocation patterning in FCC crystals based on the updated CDD model. Some key findings from these investigations were: 1) The patterning of dislocations is initiated by cross slip and internal stress fluctuations, and the refinement of the pattern results from junction formation. 2) Patterning is more prominent under high stress. 3) The correlation stress was found to be a significant part of the mean field stress in continuum representations of dislocation dynamics. During the last year of the project, we have established a method for performing dislocation dynamics in inhomogeneous alloys and demonstrated the impact of composition inhomogeneity on the characteristics of initial yielding and dislocation character in BCC alloys. We also tested this method using an irradiated ferritic alloy in which the composition and dislocation loops effects are both present. In doing so, we have considered two aspects of the role of inhomogeneity, the creation of internal coherency stress due to the dependence of the lattice parameter on the local composition, and the dependence of the dislocation mobility on the local composition. These two aspects resulted in an unexpected behavior of the dislocation system, and, in turn, the yielding behavior of BCC alloys. Key findings include: 1) The composition inhomogeneity in BCC alloys alters the well-known role of screw dislocations by forcing a level of waviness on the average dislocation character, thus destroying the screw character dominance in the yielding observed in pure or homogeneous BCC metals. 2) In the case of irradiated alloys, while composition inhomogeneity by itself and dislocation loops by themselves result in some hardening, the superposition of the two mechanisms does not result in the sum of the two contributions via any known rule. The latter result contradicts the classical works related hardening via multiple mechanisms, which state that various hardening mechanisms can be added linearly or using some Pythagorean additive rule. We were able to rationalize this unexpected result by a closer loop at the origin of the hardening mechanisms themselves, which both involved long-range elastic interactions with dislocations. We reached the conclusion that the hardening resulting from the total stress associated with these two mechanisms (current work) differs from the sum of the effects of the individual stress fields (classical literature). We have also found a major flaw in the classical theory of spinodal hardening. The latter theory never considered the impact of composition undulation on the solute hardening. We have built a new general theory accounting for the effect of solute friction together with the composition undulations on the dislocation configuration at Critical Resolved Shear Stress (CRSS), which is yielding a new definition of the spinodal hardening and new different results. This work is the first to recognize the lack of the role of solute in spinodal hardening theory of alloys.

36 MATERIALS SCIENCE↗

Chemical compatibility of cartridge materials

This twelve month progress report deals with the chemical compatibility of semiconductor crystals grown in zero gravity. Specifically, it studies the chemical compatibility between TZM, a molybdenum alloy containing titanium and zirconium, and WC 103, a titanium alloy containing Niobium and Hafnium, and Gallium arsenide (GaAs) and Cadmium Zinc Tellurite (CdZnTe). Due to the health hazards involved, three approaches were used to study the chemical compatibility between the semiconductor and cartridge materials: reaction retort, thermogravimetric analysis, and bulk cylindrical cartridge containers. A scanning electron microscope with an energy dispersive X-ray analyzer was used to examine all samples after testing. The first conclusion drawn is that reaction rates with TZM were not nearly as great as they were with WC 103. Second, the total reaction between GaAs and WC 103 was almost twice that with TZM. Therefore, even though WC 103 is easier to fabricate, at least half of the cartridge thickness will be degraded if contact is made with one of the semiconductor materials leading to a loss of strength properties.

Wilcox, Roy C.↗

Flash Cracking Reactor for Waste Plastic Processing

Conversion of waste plastic to energy is a growing problem that is especially acute in space exploration applications. Moreover, utilization of heavy hydrocarbon resources (wastes, waxes, etc.) as fuels and chemicals will be a growing need in the future. Existing technologies require a trade-off between product selectivity and feedstock conversion. The objective of this work was to maintain high plastic-to-fuel conversion without sacrificing the liquid yield. The developed technology accomplishes this goal with a combined understanding of thermodynamics, reaction rates, and mass transport to achieve high feed conversion without sacrificing product selectivity. The innovation requires a reaction vessel, hydrocarbon feed, gas feed, and pressure and temperature control equipment. Depending on the feedstock and desired product distribution, catalyst can be added. The reactor is heated to the desired tempera ture, pressurized to the desired pressure, and subject to a sweep flow at the optimized superficial velocity. Software developed under this project can be used to determine optimal values for these parameters. Product is vaporized, transferred to a receiver, and cooled to a liquid - a form suitable for long-term storage as a fuel or chemical. An important NASA application is the use of solar energy to convert waste plastic into a form that can be utilized during periods of low solar energy flux. Unlike previous work in this field, this innovation uses thermodynamic, mass transport, and reaction parameters to tune product distribution of pyrolysis cracking. Previous work in this field has used some of these variables, but never all in conjunction for process optimization. This method is useful for municipal waste incinerator operators and gas-to-liquids companies.

Timko, Michael T.↗

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↗

Theoretical and kinetic modeling study of hydrazine oxidation

The present work constitutes the first theoretical and kinetic modeling study of hydrazine oxidation, which may be important for burnout in ammonia-fueled combustion. The kinetics of the oxidation of N 2 H 4 , N 2 H 3 and tHNNH by molecular oxygen were investigated via a quantum chemistry/canonical transition state theory approach. Geometries and anharmonic frequencies were obtained with density functional theory, and energies from coupled cluster calculations (CCSD(T)) extrapolated to the infinite basis set limit, with corrections for core-valence electron correlation, scalar relativistic effects, and higher level correlation up to lambda coupled cluster, CCSDT(Q) Λ . The key reactions occurred on the N 2 H 4 O 2 potential energy surface, where the results indicated a fast reaction of N 2 H 3 with HO 2 via singlet adducts to yield tHNNH + H 2 O 2 and HNN(H)O + H 2 O, while reaction on the triplet surface proceeds via a bound complex followed by a tight, submerged barrier to yield N 2 H 4 + O 2 . The results were incorporated in a detailed reaction mechanism, which was used to interpret the shock tube results from Michel and Wagner (1965) on the effect of O 2 on hydrazine conversion at 1100–1400 K. The kinetic model captured qualitatively the observed behavior, but underestimated the reaction rate under oxidizing conditions. The hydrazine pyrolysis chemistry dominated conversion at reducing conditions and/or high temperature. At oxidizing conditions and intermediate temperatures (≲ 1400 K), reactions of N 2 -amines with HO 2 and O 2 were important for the oxidation rate.

Ab initio calculations↗

Entanglement Effect and Angular Momentum Conservation in a Nonseparable Tunneling Treatment

The important, and often dominant, role of tunneling in low temperature kinetics has resulted in numerous theoretical explorations into the methodology for predicting it. Nevertheless, there are still key aspects of the derivations that are lacking, particularly for nonseparable systems in the low temperature regime, and further explorations of the physical factors affecting the tunneling rate are warranted. In this work we obtain a closed-form rate expression for the tunneling rate constant that is a direct analog of the rigid-rotor-harmonic-oscillator expression. This expression introduces a novel "entanglement factor" that modulates the reaction rate. Furthermore, we are able to extend this expression, which is valid for nonseparable systems at low temperatures, to properly account for the conservation of angular momentum. In contrast, previous calculations have considered only vibrational transverse modes and so effectively employ a decoupled rotational partition function for the orientational modes. We also suggest a simple theoretical model to describe the tunneling effects in the vicinity of the crossover temperature (the temperature where tunneling becomes the dominating mechanism). This model allows one to naturally classify, interpret, and predict experimental data. Among other things, it quantitatively explains in simple terms the so-called "quantum bobsled" effect, also known as the negative centrifugal effect, which is related to curvature of the reaction path. Taken together, the expressions obtained here allow one to predict the thermal and E-resolved rate constants over broad ranges of temperatures and energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗