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The dissociation of molecular hydrogen by helium was studied at 5500 deg K using the quasiclassical approximation. The temperature-dependent reaction cross sections were very dependent on the initial quantum states of the molecule. A rate constant was estimated for the dissociation reaction, and agreement between theory and experiment was satisfactory.
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Identifying the role of oxide supports in transition metal catalysis is critical toward our understanding of heterogeneous catalysis. The water-gas shift (WGS) reaction is a prototypical example where oxide support dictates catalytic activity, yet the cause for this remains uncertain. Herein, we show that a single descriptor—the equilibrium constant for hydroxyl formation—relates the WGS turnover frequency across disparate oxide supports. The dissimilar equilibrium constant, or oxophilicity, between early and late transition metals exemplify the utility of metal-support interfacial sites to circumvent adsorption-energy scaling restrictions, thereby providing bifunctional gains for the WGS reaction class. In relation, the equilibrium constant for hydroxyl formation is equivalent to the equilibrium constant for the formal heterolytic dissociation of hydrogen, and therefore, reflects the ability of the metal-support interface to participate in hydrogen heterolysis. The ubiquitous coexistence, yet divergent chemical behavior of homo- and heterolytically activated hydrogen renders oxide support identity central toward our understanding of hydrogenation catalysis. This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences and performed at the Environmental Molecular Sciences Laboratory in (EMSL), which is a DOE Office of Science User Facility located at the Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle. Computational resources were provided by a user proposal at the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility. N.N. would like to thank Oliver Y. Gutierrez for critical feedback during the final stage of manuscript preparation.
A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the Cl(sup 2)P(sub j) + C2Cl4 association reaction as a function of temperature (231-390 K) and pressure (3-700 Torr) in nitrogen buffer gas. The reaction is found to be in the falloff regime between third and second order over the range of conditions investigated, although the second-order limit is approached at the highest pressures and lowest temperatures. At temperatures below 300 K, the association reaction is found to be irreversible on the experimental time scale of approximately 20 m-s. The kinetic data at T is less than 300 K have been employed to obtain falloff parameters in a convenient format for atmospheric modeling. At temperatures above 330 K, reversible addition is observed, thus allowing equilibrium constants for C2Cl5 formation and dissociation to be determined. Second- and third-law analyses of the equilibrium data lead to the following thermochemical parameters for the association reaction: Delta-H(298) = -18.1 +/- 1.3 kcal/mol, Delta-H(0) = -17.6 +/- 1.3 kcal/mol, and Delta-S(298) = -27.7 +/- 3.0 cal/mol.K. In conjunction with the well-known heats of formation of Cl((sup 2)P(sub j)) and C2Cl4 the above Delta-H values lead to the following heats of formation for C2Cl5, at 298 and 0 K: Delta-H(f,298) = 8.0 +/- 1.3 kcal/mol and Delta-H(f,0) = 8.1 +/- 1.5 kcal/mol. The kinetic and thermochemical parameters reported above are compared with other reported values, and the significance of reported association rate coefficients for understanding tropospheric chlorine chemistry is discussed.
A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the Br((sup 2)P3/2) + NO2 association reaction as a function of temperature (259-432 K) pressure (12.5 - 700 Torr), and buffer gas identity (He, Ar, H2, N2, CO2, CF4, SF6). The reaction is found to be in the falloff regime between third and second order over the entire range of conditions investigated. At temperatures below 350 K, the association reaction is found to be irreversible on the time scale of the experiment (approximately 30 ms). At higher temperatures reversible addition is observed, allowing equilibrium constants for BrNO2 formation and dissociation to be determined. Second- and third-law analyses of the equilibrium data are in only fair agreement and lead to the following thermochemical parameters for the association reaction: Delta-H(298) = 19.6 +/- 1.7 kcal/mol, Delta-H(0) = -18.6 +/- 2.0 kcal/mol, Delta-S(298) = 29.3 +/- 4.2 cal/mol/K, Delta-H(sub f)(sub 298)(BrNO2) = 17.0 +/-1.8 kcal/mol(uncertainties are 2 sigma estimates of absolute accuracy). The value for Delta-H(0) determined in this study has been employed to calculate k(sub 0)(sup SC), the low-pressure third-order rate coefficient in the strong collision limit, by using the method of Troe; calculated values of k(sub 0)(sup SC) are inconsistent with experimental results unless Delta-H(0) is assigned a value near the lower limit derived from analysis of the high-temperature approach to equilibrium data, i.e. delta-H(0) approximately equals -16.6 kcal/mol. A potential source of systematic error in the calculation of both k(sub 0)(sup SC) and the absolute entropy of BrNO2 results from the complete lack of knowledge of the energies and degeneracies of the electronic states of BrNO3. The procedure developed by Troe and co-workers has been employed to extrapolate experimental falloff curves to the low- and high-pressure limits. Derived values for k(sub 0)(M,298K) in units of 10(exp -31) cm(exp 6)/sq molecule/s range from 2.75 for M = He to 6.54 for M = CO2; 2 sigma uncertainties are estimated to be +/- 20%. Values for k(sub 0)(N2,T) in units of 10(exp -31) cm(exp 6)/sq molecule/s are 5.73 at 259 K, 4.61 at 298 K, and 3.21 at 346 K; the observed temperature dependence for k(sub 0)(N2,T) is consistent with the theoretical temperature dependence for Beta(sub c)k(sub 0)(sup SC). Values for k(sub infinity)(T) in units of 10(exp -11) cu cm/molecule/s are 2.86 at 259 K, 3.22 at 298 K, and 3.73 at 346 K; 2 sigma uncertainties are estimated to be a factor of 2. Approximate falloff parameters in a convenient format for atmospheric modeling are also derived.
Time-resolved Kelvin probe force microscopy (tr-KPFM) was used to map surface potential dynamics in LAO/STO under its critical thickness, where it acts as an insulator, as polarizing and depolarizing electric fields were applied to planar electrodes in ambient conditions. Two time constants, for polarization and relaxation (i.e., depolarization) each, were derived and were shown to be independent of the direction of electrical field, revealing the reproducibility and recovery of the surfaces. Ambient aging or recent electrical history did not change the surface kinetics as determined by tr-KPFM. During polarization, the faster time constant (~3–6 s) is likely associated with the transport of H+ ions through the full length of the channel. The slower time constant (~40–50 s), on the other hand, is observed across only half the channel width near the higher-potential–more positive–electrode, which is likely associated with an electrochemical reaction such as the dissociation of water. This slower time constant drops to ~10–20 s toward the middle of the channel which could represent the transport of OH– ions. Furthermore, during relaxation, the fast time constant is consistent with polarization and is correlated to the same mechanism while the slower time constant is higher than it was during polarization and may represent the reabsorption of moisture from the atmosphere.
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The thermodynamic stability of clathrate hydrate is calculated to predict the formation conditions corresponding to a range of solar system parameters. The calculations were performed using the statistical mechanical theory developed by van der Waals and Platteeuw (1959) and existing experimental data concerning clathrate hydrate and its components. Dissociation pressures and partition functions (Langmuir constants) are predicted at low pressure for CO clathrate (hydrate) using the properties of chemicals similar to CO. It is argued that nonsolar but well constrained noble gas abundances may be measurable by the Galileo spacecraft in the Jovian atmosphere if the observed carbon enhancement is due to bombardment of the atmosphere by clathrate-bearing planetesimals sometime after planetary formation. The noble gas abundances of the Jovian satellite Titan are predicted, assuming that most of the methane in Titan is accreted as clathrate. It is suggested that under thermodynamically appropriate conditions, complete clathration of water ice could have occurred in high-pressure nebulas around giant planets, but probably not in the outer solar nebula. The stability of clathrate in other pressure ranges is also discussed.
The thermodynamic stability of clathrate hydrate is calculated to predict the formation conditions corresponding to a range of solar system parameters. The calculations were performed using the statistical mechanical theory developed by van der Waals and Platteeuw (1959) and existing experimental data concerning clathrate hydrate and its components. Dissociation pressures and partition functions (Langmuir constants) are predicted at low pressure for CO clathrate (hydrate) using the properties of chemicals similar to CO. It is argued that nonsolar but well constrained noble gas abundances may be measurable by the Galileo spacecraft in the Jovian atmosphere if the observed carbon enhancement is due to bombardment of the atmosphere by clathrate-bearing planetesimals sometime after planetary formation. The noble gas abundances of the Jovian satellite Titan are predicted, assuming that most of the methane in Titan is accreted as clathrate. It is suggested that under thermodynamically appropriate conditions, complete clathration of water ice could have occurred in high-pressure nebulas around giant planets, but probably not in the outer solar nebula. The stability of clathrate in other pressure ranges is also discussed.
NO dissociative-recombination rate coefficient temperature dependence, assuming constant transition probability at potential crossing
A hydrodynamic description of the density distributions of the ionic products of H2O and CO in the atmosphere of an H2O-dominated comet having 10% CO is given. Two models are discussed. In the first, the effecs of photodissociation, photoionization, and gas-phase reactions are considered. In the second, the effect of an internal ionization source is also included. It is found that while the observed morphology of the H2O(+) coma of Comet Kohoutek (1973f) cannot be explained by gas-phase reactions alone, it is consistent with the presence of a strong internal source of ionization, presumably an electric current flowing through the inner coma. In the latter case the number densities of H2O(+) and CO(+) remain more or less constant within the scale lengths against collisional dissociation by the electron flux of their neutrals. While the abundance ratio of CO(+) to H2O(+) remains considerably less than unity when the internal ionization source is neglected, it is significantly larger than unity when the internal ionization source is included. Consequently, even the so-called 'CO-rich' comets may in reality be H2O-dominated, provided a strong internal source of ionization is operative.
Data from the visible-airglow experiment on the Atmosphere Explorer-E satellite have been used to determine the quantum yields of O (1S) and O (1D) from the dissociative recombination of O2(+) based on a constant total recombination rate from each vibrational level. A range of values between 0.05 and 0.18 has been obtained for the quantum yield of O (1S) and shows a positive correlation with the extent of the vibrational excitation of O2(+). The quantum yield of O (1D) has been measured to be 0.9 + or - 0.2, with no apparent dependence on the vibrational distribution of O2(+).
Electron-attachment cross sections and rate constants have been measured and calculated for the dissociative attachment processes e + CFCl3 - Cl(-) + CFCl2 and e + CCl4 - Cl(-) + CCl3. Good agreement over the electron-energy range 1-200 meV is found in energy dependence between present calculated cross sections and experimental cross sections at 300 K. The same calculation, with suitable adjustment of thermal populations, was used to calculate electron-attachment rate constants in the range 50-600 K. Experimental rate constants for CFCl3 and CCl4 were measured at temperatures of 294, 404, and 496 K (CFCl3) and 294, 400, and 500 K (CCl4) using the Cavalleri electron-density sampling method. Good agreement is found between present measurements and calculations, poor agreement with flowing-afterglow Langmuir-probe (FALP) data in CFCl3 at the higher temperatures, and reasonable agreement with FALP data for CCl4.
A new model for reactive collisions is developed within the framework of a particle method, which simulates coupled vibration-dissociation (CVD) behavior in high-temperature gases. The fundamental principles of particle simulation methods are introduced with particular attention given to the probability functions employed to select thermal and reactive collisions. Reaction probability functions are derived which favor vibrationally excited molecules as reaction candidates. The new models derived here are used to simulate CVD behavior during thermochemical relaxation of constant-volume O2 reservoirs, as well as the dissociation incubation behavior of postshock N2 flows for comparisons with previous models and experimental data.
Thermal dissociation rates for hydroperoxyalkyl (•QOOH) radicals are challenging to measure due to their inherent instability. Recent dynamics experiments have demonstrated that in situ synthesis of •QOOH radicals in a supersonic expansion in combination with IR action spectroscopy provides an effective route to accurately map their energy-resolved dissociation rates. Collaborative theoretical analyses provide a route for converting from those microcanonical rates to accurate temperature- and pressure-dependent thermal rate constants. Here, we present the results of this conversion for the dissociation of two isopentyl β-QOOH isomers of relevance to isopentane oxidation. The results are compared with existing literature values, as well as with results obtained in a similar fashion for related •QOOH systems. Extrapolations from benchmark calculations of barrier properties for smaller systems to accurate predictions for larger systems and multidimensional hindered rotor treatments are both shown to be important components of the theoretical analysis. For completeness, we extend the theoretical analysis to a treatment of the full RO 2 /QOOH system for isopentyl (1,1-dimethyl-propyl) radical.
The isothermal kinetics of H2, H2S, and O2 chemisorption onto epitaxially grown (III) oriented Fe films were studied. The measurements were made using the techniques of chemisorption induced resistance change and Auger electron spectroscopy (for adsorbed sulfur and oxygen). Also the origin of the chemisorption induced resistance change for these systems and its applicability to kinetic measurements were established. The chemisorption kinetics were interpreted as dissociative chemisorption via an adsorbed molecular species. The applicable rate constants were established. In none of the studies were the rate constants observed to be coverage dependent. By comparing the temperature dependence of the rate constants with absolute rate theory, the binding energies and activation energies of all the kinetic processes were obtained for the H2/Fe system. The initial sticking coefficient was pressure dependent for both the H2/Fe and H2S/Fe systems. This results from the step between the adsorbed molecular state and the dissociated chemisorbed state being the rate limiting step for absorption at certain pressures and temperatures. Estimates were obtained for the temperature dependence of the rate constants for the O2/Fe system.
Radical-radical reaction channels are important in the pyrolysis and oxidation chemistry of perfluoroalkyl substances (PFAS). In particular, unimolecular dissociation reactions within unbranched n-perfluoroalkyl chains, and their corresponding reverse barrierless association reactions, are expected to be significant contributors to the gas-phase thermal decomposition of families of species such as perfluorinated carboxylic acids and perfluorinated sulfonic acids. Unfortunately, experimental data for these reactions are scarce and uncertain. Furthermore, obtaining reliable theoretical predictions for such reactions is a laborious and computationally intensive task. Here, in this work, the chemical kinetics of the various association/decomposition reactions producing/decomposing the C 2 -C 4 series of unbranched n-perfluoroalkanes (C 2 F 6 , C 3 F 8 , and C 4 F 10 ) are examined using state-of-the-art ab initio transition-state-theory-based master-equation calculations. The variable-reaction-coordinate transition-state theory (VRC-TST) formalism is employed in computing the microcanonical and canonical rates for the association reactions. Reaction thermochemistry is obtained via composite quantum chemistry calculations and the laddering of error-canceling reaction schemes via a connectivity-based hierarchy approach employing ANL1/ANL0-style reference energies. Lennard-Jones collision model parameters for the considered systems were estimated by a direct dynamics approach, and collisional energy transfer parameters were obtained from analogies to systems of similar size and heavy-atom connectivity. A one-dimensional master equation approach was used to convert the microcanonical rate coefficients from the VRC-TST analysis into temperature- and pressure-dependent rate constants for the association reactions and the reverse dissociation reactions. The data are reported in standardized formats for usage in comprehensive chemical kinetic models for PFAS thermal destruction.
Dimethyl disulfide (DMDS), one of the smallest organic molecules with an S–S bond, serves as a model system for understanding photofragmentation in polypeptides and proteins. Prior studies of DMDS photodissociation excited at ∼266 nm and ∼248 nm have elucidated the mechanisms of S–S and C–S bond cleavage, which involve the lowest excited electronic states S 1 and S 2 . Far less is known about the dissociation mechanisms and electronic structure of relevant excited states of DMDS excited at ∼200 nm. Herein we present calculations of the electronic structure and properties of electronic states S 1 –S 6 accessed when DMDS is excited at ∼200 nm. Our analysis includes a comparison of theoretical and experimental UV spectra, as well as theoretically predicted one-dimensional cuts through the singlet and triplet potential energy surfaces along the S–S and C–S bond dissociation coordinates. Finally, we present calculations of spin–orbit coupling constants at the Franck–Condon geometry to assess the likelihood of ultrafast intersystem crossing. We show that choosing an accurate yet computationally efficient electronic structure method for calculating the S 0 –S 6 potential energy surfaces along relevant dissociation coordinates is challenging due to excited states with doubly excited character and/or mixed Rydberg-valence character. Our findings demonstrate that the extended multi-state complete active space second-order perturbation theory (XMS-CASPT2) balances this computational efficiency and accuracy, as it captures both the Rydberg character of states in the Franck–Condon region and multiconfigurational character toward the bond-dissociation limits. In conclusion, we compare the performance of XMS-CASPT2 to a new variant of equation of motion coupled cluster theory with single, double, and perturbative triple corrections, EOM-CCSD(T)(a)*, finding that EOM-CCSD(T)(a)* significantly improves the treatment of doubly excited states compared to EOM-CCSD, but struggles to quantitatively capture asymptotic energies along bond dissociation coordinates for these states.