Evaluated Kinetic and Photochemical Data for Atmospheric Chemistry: Supplement I CODATA Task Group on Chemical Kinetics

Baulch, D. L.; Cox, R. A.; Crutzen, P. J.; Hampson, R. F.; Kerr, J. A.; Troe, J.; Watson, Robert

doi:10.1063/1.555664

Cited by 466 publications

(146 citation statements)

References 2 publications

Supporting

Mentioning

134

Contrasting

Unclassified

Order By: Relevance

“…This number is in good agreement with the value of 1.5 × 10 -11 cm 3 /s reported by Watson and coworkers. 29 Etching Polyimide Films. We have etched polyimide films with the parallel-plate device used in the present study.…”

Section: Concentration Of the Reactive Species Shown Inmentioning

confidence: 99%

Reaction Chemistry in the Afterglow of an Oxygen−Helium, Atmospheric-Pressure Plasma

et al. 2000

View full text Add to dashboard Cite

The reaction chemistry in the afterglow of a non-equilibrium, capacitive discharge, operated at 600 Torr total pressure with (0.5 to 5.0) × 10 17 cm -3 of oxygen in helium, has been examined by ultraviolet absorption spectroscopy, optical emission spectroscopy, and numerical modeling. The densities of the active species,and O 3 , have been determined as a function of the operating conditions. At RF power densities between 6.1 and 30.5 W/cm 3 and a neutral temperature of 100 ( 40°C, the plasma generated (0.2 to 1.0) × 10 16 cm -3 of O( 3 P) and O 2 ( 1 ∆ g ), (0.2 to 2.0) × 10 15 cm -3 of O 2 ( 1 Σ g + ), and (0.1 to 4.0) × 10 15 cm -3 of O 3 . After the power was turned off, the singlet-sigma and singlet-delta states decayed within 0.1 and 30.0 ms, respectively. The concentration of oxygen atoms remained constant for about 0.5 ms, then fell rapidly due to recombination with O 2 to form O 3 . It was found that the etching rate of polyimide correlated with the concentration of oxygen atoms in the afterglow, indicating that the O atoms were the active species involved in this process.

show abstract

Section: Concentration Of the Reactive Species Shown Inmentioning

confidence: 99%

Reaction Chemistry in the Afterglow of an Oxygen−Helium, Atmospheric-Pressure Plasma

et al. 2000

View full text Add to dashboard Cite

show abstract

“…The US and the CUS rate constants lead to substantial improvement in the results giving similar results to QCT 23,24 and the experiment. [10][11][12][13]22 We should note that the tunneling contribution to the VTST rate constants has been found to be negligible even at low temperatures where the transmission coefficient calculated using the small-curvature tunneling scheme 49 is found to be between 1.01 and 1.03. The recomended experimental value at room temperature for the activation energy 22,37 is E a = 0.9 kcal mol -1 , whereas the QCT and US values are 0.75 and 0.64 kcal mol -1 , respectively.…”

Section: Resultsmentioning

confidence: 99%

“…[10][11][12][13]22 We should note that the tunneling contribution to the VTST rate constants has been found to be negligible even at low temperatures where the transmission coefficient calculated using the small-curvature tunneling scheme 49 is found to be between 1.01 and 1.03. The recomended experimental value at room temperature for the activation energy 22,37 is E a = 0.9 kcal mol -1 , whereas the QCT and US values are 0.75 and 0.64 kcal mol -1 , respectively. Thus, the experiment predicts a larger slope than the theoretical calculations, and probably a slight modification in the entrance channel of the DMBE potential energy surface would improve the results.…”

Section: Resultsmentioning

confidence: 99%

“…[1][2][3][4][5] Both reactions have been extensively studied because of their environmental implications, and experimental thermal rate constants are well-known. [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] The recommended value 21,22 for reaction R1 at room temperature is 2.8 × 10 -11 cm 3 s -1 with an estimated Arrhenius activation energy of 0.9 kcal mol -1 . The reaction H + O 3 f HO 2 + O competes with R1.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A VTST Study of the H + O₃ and O + HO₂ Reactions Using a Six-dimensional DMBE Potential Energy Surface for Ground State HO₃

Fernández‐Ramos

Varandas

2002

J. Phys. Chem. A

View full text Add to dashboard Cite

The variational transition state theory (VTST) is used to calculate thermal rate constants for the reactions H + O 3 f OH + O 2 (R1) and O + HO 2 f OH + O 2 (R2). Both reactions are studied using a double manybody expansion (DMBE) potential energy surface for ground state HO 3 . The VTST results are compared with quasiclassical trajectory calculations (QCT) and experiment. Reaction R1 shows a planar transition state which, including the zero-point energy, is 0.16 kcal mol -1 above the reactants. This reaction presents two maxima in the vibrational adiabatic potential, and hence, unified statistical theory in its canonical (CUS) and microcanonical (US) versions has been employed in addition to the canonical (CVT) and microcanonical (µVT) variational transition state theories. The results obtained by the CUS and US methods compare well with QCT and experiment. The DMBE potential energy surface predicts that reaction R2 occurs via oxygen abstraction. Two possible reaction paths were found for this reaction. One path has no transition state with an oxygen angle of attack close to 155°, and the other path presents a transition state with an oxygen angle of attack of about 80°. Because the potential energy surface for this reaction is quite flat, the CVT and µVT methods were used together with an algorithm that reorients the dividing surface to maximize the Gibbs free energy. The VTST results are found to agree reasonably well with experiment and with QCT calculations.

show abstract

“…As benchmark results, we use experimental data [105][106][107][108][109][110][111][112][113][114][115][116][117][118][119][120] corrected for zero-point vibrations, spin-orbit coupling, corevalence effects, and scalar relativistic effects 121 . In Fig.…”

Section: B the Atomization Energiesmentioning

confidence: 99%

Assessment of multireference approaches to explicitly correlated full configuration interaction quantum Monte Carlo

Kersten

Booth

Alavi

2016

The Journal of Chemical Physics

View full text Add to dashboard Cite

The Full Configuration Interaction Quantum Monte Carlo (FCIQMC) method has proved able to provide nearexact solutions to the electronic Schrödinger equation within a finite orbital basis set, without relying on an expansion about a reference state. However, a drawback to the approach is that being based on an expansion of Slater determinants, the FCIQMC method suffers from a basis set incompleteness error that decays very slowly with the size of the employed single particle basis. The FCIQMC results obtained in a small basis set can be improved significantly with explicitly correlated techniques. Here, we present a study that assesses and compares two contrasting 'universal' explicitly correlated approaches that fit into the FCIQMC framework; the [2] R12 method of Valeev et al., and the explicitly correlated canonical transcorrelation approach of Yanai et al. The former is an a posteriori internally-contracted perturbative approach, while the latter transforms the Hamiltonian prior to the FCIQMC simulation. These comparisons are made across the 55 molecules of the G1 standard set. We found that both methods consistently reduce the basis set incompleteness, for accurate atomization energies in small basis sets, reducing the error from 28 mE h to 3-4 mE h . While many of the conclusions hold in general for any combination of multireference approaches with these methodologies, we also consider FCIQMC-specific advantages of each approach.

show abstract

Evaluated Kinetic and Photochemical Data for Atmospheric Chemistry: Supplement I CODATA Task Group on Chemical Kinetics

Abstract: Erratum: The NBS tables of chemical thermodynamic properties. Selected values for inorganic and C 1 and C 2 organic substances in SI units [

Cited by 466 publications

References 2 publications

Reaction Chemistry in the Afterglow of an Oxygen−Helium, Atmospheric-Pressure Plasma

Reaction Chemistry in the Afterglow of an Oxygen−Helium, Atmospheric-Pressure Plasma

A VTST Study of the H + O₃ and O + HO₂ Reactions Using a Six-dimensional DMBE Potential Energy Surface for Ground State HO₃

Assessment of multireference approaches to explicitly correlated full configuration interaction quantum Monte Carlo

Contact Info

Product

Resources

About

Evaluated Kinetic and Photochemical Data for Atmospheric Chemistry: Supplement I CODATA Task Group on Chemical Kinetics

Abstract: Erratum: The NBS tables of chemical thermodynamic properties. Selected values for inorganic and C 1 and C 2 organic substances in SI units [

Cited by 466 publications

References 2 publications

Reaction Chemistry in the Afterglow of an Oxygen−Helium, Atmospheric-Pressure Plasma

Reaction Chemistry in the Afterglow of an Oxygen−Helium, Atmospheric-Pressure Plasma

A VTST Study of the H + O3 and O + HO2 Reactions Using a Six-dimensional DMBE Potential Energy Surface for Ground State HO3

Assessment of multireference approaches to explicitly correlated full configuration interaction quantum Monte Carlo

Contact Info

Product

Resources

About

A VTST Study of the H + O₃ and O + HO₂ Reactions Using a Six-dimensional DMBE Potential Energy Surface for Ground State HO₃