Active Thermochemical Tables: the thermophysical and thermochemical properties of methyl, CH
            <sub>3</sub>
            , and methylene, CH
            <sub>2</sub>
            , corrected for nonrigid rotor and anharmonic oscillator effects

Ruščić, Branko; Bross, David H.

doi:10.1080/00268976.2021.1969046

Cited by 40 publications

(57 citation statements)

References 95 publications

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“…The interaction of N with the ground state of molecular oxygen on the sextet PES [pathway (c)] is the only endothermic pathway among the considered ones. Notice that the calculated Δ r H o value for pathway (a) (−1.159 eV) is fairly close to that adopted in the Active Thermochemical Tables (−1.37 eV).…”

Section: Resultssupporting

confidence: 76%

Reaction of the N Atom with Electronically Excited O₂ Revisited: A Theoretical Study

2021

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The kinetics of the reaction of N with electronically excited O 2 (singlet a 1 Δ g and b 1 Σ g + states), potentially relevant for NO x formation in nonthermal air plasma, is theoretically studied using the multireference second-order perturbation theory. The corresponding thermodynamically and kinetically favored reaction pathways together with possible intersystem crossings are identified. It has been revealed that the energy barrier for the N + O 2 (a 1 Δ g ) → NO + O reaction is approximately twice the barrier height for the counterpart process with O 2 (X 3 Σ g − ). The molecular oxygen in the b 1 Σ g + state, in turn, proved to be even less reactive to atomic nitrogen than O 2 (a 1 Δ g ). Appropriate thermal rate constants for specified reaction channels are calculated by the variational transition-state theory incorporating corrections for the tunneling effect, nonadiabatic transitions, and anharmonicity of vibrations for transition states and reactants. The corresponding threeparameter Arrhenius expressions for the broad temperature range (T = 300−4000 K) are reported. At last, post-transition-state molecular dynamics simulations indicate that the N + O 2 (a 1 Δ g ) reaction produces vibrationally much colder NO molecules than the N + O 2 (X 3 Σ g − ) process.

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Section: Resultssupporting

confidence: 76%

Reaction of the N Atom with Electronically Excited O₂ Revisited: A Theoretical Study

2021

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“…We obtain virtually the same strain energies for cyclopentane (6.13 kcal/mol), cyclobutane (25.82 kcal/mol), and cyclopropane (26.95 kcal/mol), if we employ experimental heats of formation …”

Section: Applicationsmentioning

confidence: 99%

“…Deviation of BEBOP’s relative energies (shown in parentheses) of the C 4 H 6 isomers compared to experimental energies in kcal/mol. All experimental relative energies were obtained from ref , except for the experimental relative energies of methylenecyclopropane, bicyclobutane, and methylcyclopropene obtained from ref .…”

Section: Applicationsmentioning

confidence: 99%

“…Deviation (theory–experiment) of BEBOP’s bond dissociation energy (shown in parentheses) to the experimental bond dissociation energies from an active thermochemical table (ATcT , ) found in ref for various small hydrocarbons. The BEBOP net bond energies for each chemical species are shown next to the chemical bonds, and curly arrows represent antibonding interactions.…”

Section: Introductionmentioning

confidence: 99%

“…Deviation of BEBOP’s BDE energy to experimental energies in kcal/mol from species used in our test set. All experimental D 0 were obtained from ref , except compounds containing B and (CH 3 ) 3 COOH, which were obtained from ROCBS-QB3.…”

Section: Introductionmentioning

confidence: 99%

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A Bond-Energy/Bond-Order and Populations Relationship

Zulueta

Tulyani

Westmoreland

et al. 2022

J. Chem. Theory Comput.

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We report an analytical bond energy from bond orders and populations (BEBOP) model that provides intramolecular bond energy decompositions for chemical insight into the thermochemistry of molecules. The implementation reported here employs a minimum basis set Mulliken population analysis on well-conditioned Hartree–Fock orbitals to decompose total electronic energies into physically interpretable contributions. The model’s parametrization scheme is based on atom-specific parameters for hybridization and atom pair-specific parameters for short-range repulsion and extended Hückel-type bond energy term fitted to reproduce CBS-QB3 thermochemistry data. The current implementation is suitable for molecules involving H, Li, Be, B, C, N, O, and F atoms, and it can be used to analyze intramolecular bond energies of molecular structures at optimized stationary points found from other computational methods. This first-generation model brings the computational cost of a Hartree–Fock calculation using a large triple-ζ basis set, and its atomization energies are comparable to those from widely used hybrid Kohn–Sham density functional theory (DFT, as benchmarked to 109 species from the G2/97 test set and an additional 83 reference species). This model should be useful for the community by interpreting overall ab initio molecular energies in terms of physically insightful bond energy contributions, e.g., bond dissociation energies, resonance energies, molecular strain energies, and qualitative energetic contributions to the activation barrier in chemical reaction mechanisms. This work reports a critical benchmarking of this method as well as discussions of its strengths and weaknesses compared to hybrid DFT (i.e., B3LYP, M062X, PBE0, and APF methods), and other cost-effective approximate Hamiltonian semiempirical quantum methods (i.e., AM1, PM6, PM7, and DFTB3).

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Automated reaction kinetics and network exploration (Arkane): A statistical mechanics, thermodynamics, transition state theory, and master equation software

Dana

Johnson

Allen

et al. 2023

Int J of Chemical Kinetics

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The open-source statistical mechanics software described here, Arkane-Automated Reaction Kinetics and Network Exploration-facilitates computations of thermodynamic properties of chemical species, high-pressure limit reaction rate coefficients, and pressure-dependent rate coefficient over multi-well molecular potential energy surfaces (PES) including the effects of collisional energy transfer on phenomenological kinetics. Arkane can use estimates to fill in information for molecules or reactions where quantum chemistry information is missing. The software solves the internal energy master equation for complex unimolecular reaction systems. Inputs to the software include converged electronic structure computations performed by the user using a variety of supported software packages (Gaussian, Molpro, Orca, TeraChem, Q-Chem, Psi4). The software outputs high-pressure limit rate coefficients and pressure-dependentThis is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

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Active Thermochemical Tables: the thermophysical and thermochemical properties of methyl, CH ₃ , and methylene, CH ₂ , corrected for nonrigid rotor and anharmonic oscillator effects

Cited by 40 publications

References 95 publications

Reaction of the N Atom with Electronically Excited O₂ Revisited: A Theoretical Study

Reaction of the N Atom with Electronically Excited O₂ Revisited: A Theoretical Study

A Bond-Energy/Bond-Order and Populations Relationship

Automated reaction kinetics and network exploration (Arkane): A statistical mechanics, thermodynamics, transition state theory, and master equation software

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Active Thermochemical Tables: the thermophysical and thermochemical properties of methyl, CH 3 , and methylene, CH 2 , corrected for nonrigid rotor and anharmonic oscillator effects

Cited by 40 publications

References 95 publications

Reaction of the N Atom with Electronically Excited O2 Revisited: A Theoretical Study

Reaction of the N Atom with Electronically Excited O2 Revisited: A Theoretical Study

A Bond-Energy/Bond-Order and Populations Relationship

Automated reaction kinetics and network exploration (Arkane): A statistical mechanics, thermodynamics, transition state theory, and master equation software

Contact Info

Product

Resources

About

Active Thermochemical Tables: the thermophysical and thermochemical properties of methyl, CH ₃ , and methylene, CH ₂ , corrected for nonrigid rotor and anharmonic oscillator effects

Reaction of the N Atom with Electronically Excited O₂ Revisited: A Theoretical Study

Reaction of the N Atom with Electronically Excited O₂ Revisited: A Theoretical Study