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Results for “Reaction path analysis”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

A comprehensive experimental and kinetic modeling study of di-isobutylene isomers: Part 1

We report di-isobutylene has received significant attention as a promising fuel blendstock, as it can be synthesized via biological routes and is a short-listed molecule from the Co-Optima initiative. Di-isobutylene is also popularly used as an alkene representative in multi-component surrogate models for engine studies of gasoline fuels. However, there is limited experimental data available in the literature for neat di-isobutylene under engine-like conditions. Hence, most existing di-isobutylene models have not been extensively validated, particularly at lower temperatures (< 1000 K). Most gasoline surrogate models include the di-isobutylene sub-mechanism published by Metcalfe et al. with little or no modification. The current study is undertaken to develop a detailed kinetic model for di-isobutylene and validate the model using a wide range of relevant experimental data. Part 1 of this study exclusively focuses on the low- to intermediate temperature kinetics of di-isobutylene. An upcoming part 2 discusses the high-temperature model development and validation of the relevant experimental targets. Ignition delay time measurements for the di-isobutylene isomers were performed at pressures ranging from 15 - 30 bar at equivalence ratios of 0.5, 1.0, and 2.0 diluted in air and in the temperature range 650 - 900 K using two independent rapid compression machine facilities. In addition, measurements of species identified during the oxidation of these isomers were performed in a jet-stirred reactor and in a rapid compression machine. A detailed kinetic model for the di-isobutylene isomers is developed to capture the wide range of new experimental targets. For the first time, a comprehensive low-temperature chemistry submodel is included. The differences in the important reaction pathways for the accurate prediction of the oxidation of the two DIB isomers are compared using reaction path analysis. In conclusion, the most sensitive reactions controlling the ignition delay times of the DIB isomers under the pressure and temperature conditions necessary for autoignition in engines are identified.

09 BIOMASS FUELS↗
DOE OSTI2021

Ignition delay times of NH 3 /DME blends at high pressure and low DME fraction: RCM experiments and simulations

Here, autoignition delay times of ammonia/dimethyl ether (NH 3 /DME) mixtures were measured in a rapid compression machine with DME fractions of 0, 2 and 5 and 100% in the fuel. The measurements were performed at equivalence ratios $\varphi$= 0.5, 1.0 and 2.0 and pressures in the range 10–70 bar; depending on the fuel composition, the temperatures after compression varied from 610 K to 1180 K. Admixture of DME is seen to have a dramatic effect on the ignition delay time, effectively shifting the curves of ignition delay vs. temperature to lower temperatures, up to ~250 K compared to pure ammonia. Two-stage ignition is observed at $\varphi$= 1.0 and 2.0 with 2% and 5% DME in the fuel, despite the pressure being higher than that at which pure DME shows two-stage ignition. At $\varphi$= 0.5, a reproducible pre-ignition pressure rise is observed for both DME fractions, which is not observed in the pure fuel components. A novel NH 3 /DME mechanism was developed, including modifications in the NH 3 subset and addition of the NH 2 + CH 3 OCH 3 reaction, with rate coefficients calculated from ab initio theory. Simulations faithfully reproduce the observed pre- ignition pressure rise. While the mechanism also exhibits two-stage ignition for NH 3 /DME mixtures, both qualitative and quantitative improvement is recommended. The overall ignition delay times for ammonia/DME mixtures are predicted well, generally being within 50% of the experimental values, although reduced performance is observed for pure ammonia at $\varphi$= 2.0. Simulating the ignition process, we observe that the DME is oxidized much more rapidly than ammonia. Analysis of the mechanism indicates that this ‘early DME oxidation’ generates reactive species that initiate the oxidation of ammonia, which in turn begins heat release that raises the temperature and accelerates the oxidation process towards ignition. The reaction path analysis shows that the low-temperature chain-branching reactions of DME are important in the early oxidation of the fuel, while the sensitivity analysis indicates that several reactions in the oxidation of DME, including cross reactions between DME and NH 3 species presented here, are critical to ignition, even at fractions of 2% DME in the fuel.

10 SYNTHETIC FUELS↗
DOE OSTI2024

Flame kinetics at scramjet-engine-relevant conditions: Role of prompt dissociation of weakly-bound radicals

Combustion in high-speed ram-based propulsion engines occurs under distinct thermodynamic conditions of high reactant temperatures (greater than 1000 K) and relatively low pressures (<5 atm). There is a lack of fundamental flame measurements at such conditions that result in adiabatic flame temperatures (T ad ) exceeding 2500 K. In this work, we have measured laminar flame speeds of oxygen-enriched CH 4 /oxidizer mixtures at sub-atmospheric conditions to probe kinetics at high T ad using the isobaric spherically expanding flame approach. Simulations with recent kinetic models revealed increasing differences between data and model predictions with increasing T ad , reaching up to 25 %. Kinetic analyses reveal that at the thermodynamic conditions in these O 2 -enriched flames, i.e., lower pressures and higher T ad , the effects of HCO prompt dissociation are accentuated. In addition to HCO, the prompt dissociations of CH 2 OH and C 2 H 5 are also considered. Here, the prompt dissociations of all three radicals were evaluated and their effects considered in flame speed simulations. Reaction path analysis for the present flames revealed that approximately half of the reaction flux for HCO formation undergoes prompt dissociation to H + CO. Furthermore, these analyses also revealed that the pathways and sensitive reactions are similar between oxygen-enriched fuel/oxidizer mixtures and preheated fuel/air mixtures, if both have similar T ad . Thus, flames of oxygen-enriched mixtures could be a surrogate to probe the flame chemistry of highly preheated mixtures at relatively low pressures that are often encountered in ram-based propulsion engine combustors.

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

Influence of the double bond position in combustion chemistry of methyl butene isomers: A shock tube and laser absorption study

Shock tube experiments have been carried out on 2–methyl–1–butene (2M1B), 2–methyl–2–butene (2M2B), and 3–methyl–1–butene (3M1B)—the three isomers of methyl butene compound. Here, carbon monoxide (CO) time–histories and ignition delay times are obtained behind reflected shockwaves over the temperature range of 1350–1630 K and pressures of 8.3–10.5 atm with stoichiometric mixtures of 0.075% fuel in O 2 /Ar. Comparative ignition study reveals that 3M1B ignites significantly faster than the other two isomers, while 2M1B dissociates earlier but ignites later than 2M2B. Possible mechanisms for this behavior are discussed with ignition delay time sensitivity and reaction path analysis. In addition, time–resolved CO measurements are compared with three different reaction mechanisms from the literature. Sensitivity analyses have been carried out to identify important reactions that need attention to accurately predict the chemistry of these isomers. Further investigation into the rates of unimolecular fuel decomposition reactions and C 3 H 3 + O 2 = CH 2 CO + HCO reaction are suggested based on the current investigation.

09 BIOMASS FUELS↗
DOE OSTI2022

Numerical Study of PAHs and Soot Emissions from Gasoline–Methanol, Gasoline–Ethanol, and Gasoline– n -Butanol Blend Surrogates

Soot formation is an intricate phenomenon, and soot propensity of a fuel is interwoven with the fuel composition, physical and chemical properties, and combustion environment. Here, the present study examines the hypothesis that in addition to the chemical composition of the fuel, the sooting nature of the fuel is closely coupled with its chemical property known as octane sensitivity (S). With this motivation, the present study numerically investigates the effects of gasoline surrogate composition and its property, octane sensitivity (S), on polycyclic aromatic hydrocarbons (PAHs) and soot emissions. Four-component toluene primary reference fuel (TPRF)–alcohol blends, comprising iso-octane, n-heptane, toluene, and one of the three different alcohols- methanol, ethanol, and n-butanol, are used as gasoline surrogates. A total of 320 TPRF–alcohol mixtures, with S in the range of 1–10, are examined under laminar counterflow diffusion flame conditions. A detailed chemical mechanism coupled with a comprehensive soot model, which includes reactions for soot inception, surface growth, PAH condensation, and oxidation, is adopted. The analysis indicates that the toluene content in the fuel mixture has a prominent effect, while the alcohol content and octane sensitivity of the fuel have a weak correlation with the PAHs and soot. Thus, it is not clear if any of these three variables, namely, toluene content in the fuel, alcohol content in the fuel, and S, are individually sufficient to characterize the PAHs and soot across various blends. For this reason, a new variable (X CHO ) based on the elemental composition of the fuel mixture is identified and it is shown that X CHO along with S of the fuel characterize soot emissions satisfactorily. Further, a reaction path analysis indicates that the efficacy of alcohols in reducing soot emissions follows the order: methanol > ethanol > n-butanol.

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

Ethylene oxidation on unpromoted silver catalysts: Reaction pathway and selectivity analysis using DFT calculations

Chemical conversions in catalytic partial oxidation processes of light hydrocarbons are responsible for the production of numerous industrial chemicals, plastics, and intermediates. These processes are relatively expensive to perform, and are typically operated at high thermodynamic inefficiency, so the development of novel, highly efficient catalysts would prove to be very cost effective. Herein, our study focused on surface catalytic mechanisms of the ethylene oxide (EO) formation process. Periodic plane-wave Density Functional Theory (DFT) methods were used to analyze related reaction mechanisms on the Ag(111) surface facet with low coverage. Energetic changes of related species and pathways were calculated. Key surface species are identified to suggest the factors for the observed selectivity during EO formation. Our results are consistent with previous kinetic modeling efforts in the literature which did not employ DFT analysis. Lastly, our study demonstrates how fundamental theoretical investigations and multi-scale modeling techniques are currently impacting the advancement of rational catalyst design and microkinetic modeling techniques in the light hydrocarbon processing industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

An experimental and kinetic modeling study of the ignition of 2-methyl decane

Ignition delay times (IDTs) of 2-methyl decane (C 11 H 24 -2) are measured in a high-pressure shock tube and in a rapid compression machine at equivalence ratios in the range 0.5–2.0 at 90 % dilution, at temperatures in the range 600–1430 K and at pressures of 15 and 30 bar. To clarify the effect of the branched methyl group on fuel oxidation, IDTs of n-undecane (nC 11 H 24 ) are also measured at similar conditions to those measured for C 11 H 24 -2. A new chemical kinetic mechanism, using C3MechV4.0.1 as the core chemistry, is developed and validated against the new experimental data. The thermodynamic properties of the fuel (RH), alkyl (Ṙ), alkyl peroxy (RȮ 2 ), hydroperoxy-alkyl (Q̇OOH), and peroxy hydroperoxy alkyl (Ȯ 2 QOOH) radicals are updated in both the C 11 H 24 -2 and nC 11 H24 models using THERM25. A reaction path flux analysis for C 11 H 24 -2 at different temperatures was conducted. Compared to nC 11 H 24 , C 11 H 24 -2 shows slower reactivity. At low and intermediate temperatures, the chain propagation pathway Q̇OOH ↔ C 11 cyclic ether + ȮH is favored for C 11 H 24 -2, while the chain branching pathway Q̇OOH ↔ Ȯ 2 QOOH ↔ C 11 carbonyl hydroperoxide (KHP) + ȮH is suppressed, leading to lower reactivity compared to nC 11 H 24 . At high temperatures, the presence of the branched methyl group inhibits the direct decomposition of the fuel, resulting in reduced C 2 H 4 formation, which in turn suppresses the reactivity of the fuel.

2-methyl decane↗
DOE OSTI2025

Unraveling Hydrogen Induced Geochemical Reaction Mechanisms through Coupled Geochemical Modeling and Machine Learning

Underground hydrogen storage (UHS) provides a promising large-scale, long-term energy storage solution. A reasonable recovery of stored hydrogen is critical for a successful storage scheme. However, in subsurface reservoirs hydrogen is subject to active geochemical reactions that might result in hydrogen loss. In this study, we implemented a geochemical modeling approach coupled with an unsupervised machine learning technique called non-negative matrix factorization (NMF) to unravel the complex brine-rock-H 2 geochemical processes responsible for hydrogen losses, with particular focus on sulfate reduction reactions. NMF is applied to modeled mineral evolution and fluid component profiles to retrieve profiles that can be interpreted to more easily assess competing processes. NMF decouples simulated competing equilibrium reactions. This facilitates separation of overlapping reaction profiles from redox processes, dissolution fronts, and secondary precipitation while considering the effects of simulation parameters such as salinity, temperature, and total H 2 pressure. NMF successfully discriminates these competing effects in nonlinear ways, allowing robust interpretation. In addition, NMF reveals subtle coupled mineral associations and reaction fronts that are invisible to conventional model analysis. This integrated approach strengthens the conceptual understanding of complex nonlinear hydrogen-brine-rock interactions and advances geochemical research on UHS systems to resolve complexities in modeled geochemical systems without the need for direct experiments or prior knowledge. Furthermore, this study highlights the efficacy of combining geochemical modeling with machine learning techniques to enhance the interpretability of the intricate geochemical simulation output through deciphering the overlapping reaction path that cannot be achieved only using conventional analysis of geochemical models alone.

08 HYDROGEN↗
DOE OSTI2025

Experimental and Theoretical Thermokinetic Analysis of the Na 3 VO 4 –CO 2 Reaction System under Different Physicochemical Conditions

Sodium vanadate (Na 3 VO 4 ) was synthesized, structural and microstructurally characterized as well as tested as possible carbon dioxide (CO 2 ) captor through thermodynamic calculations in addition to thermogravimetric dynamic and isothermal analyses. Ceramic structural characterization evidenced the formation of the Na 3 VO 4 crystal phase, while microstructural features evidenced dense agglomerates with a poor specific surface area, although synthesis temperature (600 °C) was not as high as that for other sodium ceramics. Na 3 VO 4 was investigated for the CO 2 capture process through dynamic and isothermal experiments, in the presence or absence of oxygen. All these experiments showed that Na 3 VO 4 possesses interesting CO 2 capture properties in a specific temperature range (520 and 600 °C). Isothermal products characterization allowed to elucidate the reaction pathway, implying the Na 4 V 2 O 7 formation, as possible reactive intermediate. In fact, reaction path evolution was supported with theoretical thermodynamic data. Moreover, the kinetic analysis, performed using the Avrami-Erofeev mathematical model and subsequent thermodynamic data obtention, probed the positive influence of the temperature, in both CO 2 superficial and bulk chemical sorption processes, while oxygen addition did not enhance the superficial process. Additionally, as it would be expected, kinetics were enhanced as a function of the CO 2 concentration.

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

CO 2 conversion to syngas via electrification of endothermal reactors: Process design and environmental impact analysis

CO 2 utilization via reverse water gas shift (rWGS) reaction has been proposed as a path to the sustainable utilization. Here this work presents a detailed process modelling study where steam methane reforming (SMR) generated hydrogen was combined with rWGS to produce syngas (CO + H 2 ) with various hydrogen-to-carbon oxide ratios. To further decrease CO 2 emissions that may offset the benefits of CO 2 converted in rWGS, electrification of endothermal reactors, both SMR and rWGS was considered where CO 2 emitting fuel burning in the furnace was replaced by the emerging ohmic (resistive) heating. Material and energy inventory obtained from process design calculations was used to perform Life Cycle Analysis (LCA) to calculate environmental impacts of CO 2 consumption and reactor electrification. The results showed that greenhouse gas emissions, in CO 2 kg equivalent, were the lowest when both SMR and rWGS were heated using wind-generated electricity, decreasing from 25 to 10 kg CO 2 equivalent for H 2 :CO = 2:1 while the conventional electricity mix used for furnace electrical heating across the board of scenarios generated highest environmental impacts, much higher than those that used natural gas as fuel. Process economics calculations suggested that, when both SMR and rWGS were electrically heated, the process only showed product syngas cost parity with the conventional fuel heated design when electricity cost was ~$0.008/kWh. This suggests that CO 2 utilization scenarios involving process electrification need to be carefully considered from the total design perspective so they do not produce more greenhouse gases than in conventional non-electrified scenarios.

42 ENGINEERING↗
DOE OSTI2022

Uncertainty quantification in breakup reactions

Breakup reactions are one of the favored probes to study loosely bound nuclei, particularly those in the limit of stability forming a halo. In order to interpret such breakup experiments, the continuum discretized coupled channel method is typically used. In this study, the first Bayesian analysis of a breakup reaction model is performed. Herein we use a combination of statistical methods together with a three-body reaction model (the continuum discretized coupled channel method) to quantify the uncertainties on the breakup observables due to the parameters in the effective potential describing the loosely bound projectile of interest. The combination of tools we develop opens the path for a Bayesian analysis of not only breakup processes, but also a wide array of complex processes that require computationally intensive reaction models.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Kinetics Modeling for Design of Continuous Enzymatic Hydrolysis

Enzymatic hydrolysis of cellulose to monomeric sugars continues to be a limiting step in cost-effectively producing sugar and fermentation-based biofuels from biomass. In particular, the high cost of enzymes coupled with the long time-scale of reaction pose challenges to economic viability. Performing enzymatic hydrolysis in a continuous mode with enzyme recycle may provide a path towards substantially reduced costs for sugar production, but design and analysis are complicated by a lack of suitable kinetics models. Computationally attainable models, such as fractal-based models, require knowledge of the reaction-history of the biomass, and are thus only suitable for describing the batch reactions from which they are derived. Fundamental models, while potentially more generalizable, are often too computationally intensive to use in process or reactor modeling. In this work, a phenomenological rate model is proposed based on a two-phase substrate representation. Good agreement is seen between batch and continuous enzymatic hydrolysis (CEH) experiment data, which validates the model and enables us to solve for reactor design parameters, such as CEH reactor size and stream flow rates, based on process variables like yield. This model is integrated with techno-economic analysis software to explore economic sensitivities. Important design optimizations and tradeoffs are identified and quantified, including the relative cost imposed by rate slowdown from sugar inhibition versus the cost to remove and concentrate sugars at a lower concentration. It also identifies, high-leverage avenues for further exploration, such as increasing the maximum feasible solids concentration, and sustaining high membrane flux and reliability.

09 BIOMASS FUELS↗
DOE OSTI2026

Understanding NBI heating and fueling in LTX-β tokamak

My work on the contract DE-SC=0023274 (July, 2022 - July, 2025) was focused on understanding the plasma fueling by NBI. On Dec. 1998 with Sergei Krasheninnikov (UCSD, San Diego, CA) we initiated the Li Wall Fusion (LiWFusion) as a new concept of magnetic fusion [1]. The new 1 2 plasma 3 4 5 6 2.1 Overview of rate coefficients, mean-free paths λH0 , and diffusions coefficients 6 2. GSV code for ⟨σv⟩ analysis of NBI fueling concept was a reaction of the lack of luck of tokamak fusion with QDT = 1 on TFTR and JET. We recognized the edge plasma cooling by recycling to be the route reason of the tokamak problems on the way to burning plasma. LiWFusion relies on plasma pumping by a lithium layer on the inner walls of the plasma chamber, combined with the plasma heating and fueling by the Neutral Beam Injection (NBI). These two innovations eliminate the route problem of the tokmak fusion. The concept became theoretically mature in 2006. In 2012, the technology of continuously Flowing Liquid Lithium (24/7-FLiLi) was invented by me for the future implementations of the LWFusion concept. At the same time, my every presentation on LiWFusion to International Symposium on Lithium Applications since 2010 was objected by some person with words “Everybody since the 1970s knows that plasma fueling by NBI is impossible”. I dropped the name of the author of this objection and ignored his views. My work on the current grant on NBI fueling of LTX-β not only clarified the issue but resolved it in an astonishing way. The NBI fueling was fully understood (thus humiliating the current dogmatic fusion community). The new future of LTX-β dedicated for decades to Li in tokamaks, as well as of the entire magnetic fusion program was envisioned, in sharp contrast with the fallure of OFES in the post-TFTR era of 21st century.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Concepts Relevant for the Kinetic Analysis of Reversible Reaction Systems

The net rate of a reversible chemical reaction is the difference between unidirectional rates of traversal along forward and reverse reaction paths. In a multistep reaction sequence, the forward and reverse trajectories, in general, are not the microscopic reverse of one another; rather, each unidirectional route is comprised of distinct rate-controlling steps, intermediates, and transition states. Consequently, traditional descriptors of rate (e.g., reaction orders) do not reflect intrinsic kinetic information but instead conflate unidirectional contributions determined by (i) the microscopic occurrence of forward/reverse reactions (i.e., unidirectional kinetics) and (ii) the reversibility of reaction (i.e., nonequilibrium thermodynamics). This review aims to provide a comprehensive resource of analytical and conceptual tools which deconvolute the contributions of reaction kinetics and thermodynamics to disambiguate unidirectional reaction trajectories and precisely identify rate- and reversibility-controlling molecular species and steps in reversible reaction systems. The extrication of mechanistic and kinetic information from bidirectional reactions is accomplished through equation-based formalisms (e.g., De Donder relations) grounded in principles of thermodynamics and interpreted in the context of theories of chemical kinetics developed in the past 25 years. Here, the aggregate of mathematical formalisms detailed herein is general to thermochemical and electrochemical reactions and encapsulates a diverse body of scientific literature encompassing chemical physics, thermodynamics, chemical kinetics, catalysis, and kinetic modeling.

42 ENGINEERING↗
DOE OSTI2021

Electrochemical Decomposition of Primary Alcohol Groups in Deep Eutectic Solvents

This work investigates the electrochemical decomposition of an ethylene glycol/sodium chloride electrolyte and a deep eutectic solvent (DES) comprised of ethylene glycol/choline chloride (ethaline). Understanding these reactions can help to better understand the safety risks of overcharge when these electrolytes are used in a battery and to guide the design of DES electrolytes for improved electrochemical stability. Analysis of the decomposition products was performed using a combination of coulometry, gas chromatography, mass spectrometry, and Fourier transform infrared spectroscopy. It was found that even at relatively low (mM) concentrations of water, a stoichiometric rate of hydrogen is produced under cathodic conditions in both the ethaline and EG/NaCl electrolytes. This suggest an electrochemical hydrolysis cathodic decomposition reaction that produces both hydrogen gas and hydroxyl ions. This reaction was verified in both electrolytes by also identifying the liquid phase products. Only liquid phase products were observed under anodic conditions. A suspected alcohol oxidation to aldehyde anodic decomposition reaction was confirmed through a similar analysis of products. A tertiary alcohol only DES was investigated to eliminate these decomposition paths and was found to have increased stability window compared to the primary alcohol.

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

Path to Increasing p-B11 Reactivity via ps and ns Lasers

The Lawson criterion for proton-boron (p-11B) thermonuclear fusion is substantially higher than that for deuterium-tritium (DT) because the fusion cross section is lower and peaks at higher ion energies. The Maxwellian averaged p-11B reactivity peaks at several hundred keV, where bremsstrahlung radiation emission may dominate over fusion reactions if electrons and ions are in thermal equilibrium and the losses are unrestricted. Nonequilibrium burn has often been suggested to realize the benefits of this aneutronic reaction, but the predominance of elastic scattering over fusion reactivity makes this difficult to achieve. The development of ultrashort pulse lasers (USPL) has opened new possibilities for initiating nonequilibrium thermonuclear burns and significant numbers of p-11B alpha particles have been reported from several experiments. We present an analysis that shows that these significant alpha yields are the result of beam fusion reactions that do not scale to net energy gain. We further find that the yields can be explained by experimental parameters and recently updated cross sections such that a postulated avalanche mechanism is not required. We use this analysis to understand the underlying physics of USPL-driven nonequilibrium fusion reactions and whether they can be used to initiate fusion burns. We conclude by outlining a path to increasing the p-11B reactivity towards the goal of achieving ignition and describing the design principles that we will use to develop a computational point design.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Solvent reaction coordinate for an S N 2 reaction

We study the prototypical S N 2 reaction Cl – + CH 3 Cl → CH 3 Cl + Cl – in water using QM/MM computer simulations with transition path sampling and inertial likelihood maximization. We have identified a new solvent coordinate that improves upon the original atom-exchange coordinate used in the classic analysis by Chandrasekhar, Smith, and Jorgensen. The new solvent coordinate quantifies instantaneous solvent induced polarization relative to equilibrium charge density at each point along the reaction pathway. In this paper, we will present free energy surfaces, transmission coefficients, and committor tests associated with this collective coordinate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗