A reduced dimension quantum reactive scattering study of OH + CO⇌H + CO2

Schatz, George C.; Dyck, Jeff

doi:10.1016/0009-2614(92)85080-t

Cited by 51 publications

(19 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The first quantum calculations of the reaction probability were done by Schatz and Dyke . They used a two-degree-of-freedom, reduced dimensionality approach in which the nonreactive CO bond was treated as a spectator.…”

Section: Resonances In Hcomentioning

confidence: 99%

“…Resonances have been calculated and characterized for a small number of important radical−radical systems. These include the simple dissociation reaction HCO → H + CO, about which much more will given below, HO 2 → H + O 2 , OH + O, − , , LiHF, − the four-atom system HOCO → OH + CO, H + CO 2 , in two, − three, , four, and five degrees of freedom, a reduced dimensionality calculation of resonances in ketene isomerization, and statistical calculations of resonances in H 2 CO, which have been measured experimentally …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Resonances: Bridge between Spectroscopy and Dynamics

Bowman

1998

J. Phys. Chem. A

View full text Add to dashboard Cite

Resonances are metastable, quasibound states of a molecular complex. They are formed predominantly by vibrational excitation of a molecular complex above a dissociation threshold. Resonances share a number of features in common with bound states, including the possibility of making spectroscopic assignments of them. Thus, resonances can be viewed as the bridge between the bound state spectrum, conventionally the domain of spectroscopy, and the continuum, which is the domain of dynamics. I review a variety of methods from a number of articles to calculate and characterize resonances, with a special focus on resonances in HCO, which have been extensively studied both theoretically and experimentally. HCO represents an extreme case, where most resonances are isolated and nonoverlapping. The effect of overall rotation on resonance positions and widths of HCO is examined in detail, and I present tests of several approximate treatments of rotation. I also point out the role that resonances play in the dynamics of unimolecular reactions, radical-radical reactions, and recombination/dissociation reactions, again using HCO as the key example. The use of "reduced dimensionality" ideas to obtain full dimensional reaction probabilities for a resonance-dominated reaction is illustrated for the OH + CO f H + CO 2 reaction, with special attention to the role of the "spectator" COstretch.

show abstract

Section: Resonances In Hcomentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Resonances: Bridge between Spectroscopy and Dynamics

Bowman

1998

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…The reaction path features deep HOCO potential wells flanked by an entrance channel bottleneck and near-isoenergetic exit barrier . Earlier dynamical studies of this reaction − were not quantitatively correct as they suffered from poor representations of the reactive PES. , In 2012, a global PES for this reaction was developed by fitting a large number of high-level ab initio points, providing a chemically accurate description of the reaction pathway and thus a much better characterization of the kinetics and reaction dynamics. − In particular, the new PES possesses a thin exit barrier, which permitted the quantum mechanical confirmation of the experimentally observed deep tunneling of cis -HOCO to the H + CO 2 products. , Subsequently (in 2013), a more accurate fit of the PES was reported by Zhang and co-workers, which was further improved (denoted as PES-2014 hereafter) using the permutation invariant polynomial neural network (PIP-NN) method . Since then, there have been several dynamical studies on this PES. − Interestingly, the calculated DCSs on the PIP-NN PES did not agree with the experimental results very well .…”

mentioning

confidence: 99%

Combined Experimental–Theoretical Study of the OH + CO → H + CO₂ Reaction Dynamics

Caracciolo

Lü

Balucani

et al. 2018

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

A combined experimental-theoretical study is performed to advance our understanding of the dynamics of the prototypical tetra-atom, complex-forming reaction OH + CO → H + CO, which is also of great practical relevance in combustion, Earth's atmosphere, and, potentially, Mars's atmosphere and interstellar chemistry. New crossed molecular beam experiments with mass spectrometric detection are analyzed together with the results from previous experiments and compared with quasi-classical trajectory (QCT) calculations on a new, full-dimensional potential energy surface (PES). Comparisons between experiment and theory are carried out both in the center-of-mass and laboratory frames. Good agreement is found between experiment and theory, both for product angular and translational energy distributions, leading to the conclusion that the new PES is the most accurate at present in elucidating the dynamics of this fundamental reaction. Yet, small deviations between experiment and theory remain and are presumably attributable to the QCT treatment of the scattering dynamics.

show abstract

“…The HOCO radical has been well characterized with quantum-chemical calculations. [35][36][37][38][39][40][41][42] We performed calculations on HOCO at the same level as for ClCOOH mainly for comparison purposes. Vibrational wavenumbers ͑in cm −1 ͒ and IR intensities ͑in km mol −1 ͒ for c-HOCO are 3562 ͑16͒, −1 , corresponding approximately to the C = O stretching and C-O stretching modes, respectively, whereas the most intense bands of t-HOCO are at 1897 and 1239 cm −1 , corresponding to the C = O stretching and COH bending modes, respectively.…”

Section: -3mentioning

confidence: 99%

Infrared absorption of gaseous c-ClCOOH and t-ClCOOH recorded with a step-scan Fourier-transform spectrometer

Chu

Lee

2009

The Journal of Chemical Physics

View full text Add to dashboard Cite

Two conformers of ClCOOH were produced upon irradiation at 355 nm of a gaseous flowing mixture of Cl(2), HCOOH, and N(2). A step-scan Fourier-transform infrared spectrometer coupled with a multipass absorption cell was utilized to monitor the transient spectra of ClCOOH. Absorption bands with origins at 1808.0 and 1328.5 cm(-1) are attributed to the C=O stretching and COH bending modes of t-ClCOOH, respectively; those at 1883.0 and 1284.9 cm(-1) are assigned as the C=O stretching and COH bending modes of c-ClCOOH, respectively. These observed vibrational wavenumbers agree with corresponding values for t-ClCOOH and c-ClCOOH predicted with B3LYP/aug-cc-pVTZ density-functional theory and the observed rotational contours agree satisfactorily with simulated bands based on predicted rotational parameters. The observed relative intensities indicate that t-ClCOOH is more stable than c-ClCOOH by approximately 3 kJ mol(-1). A simple kinetic model is employed to account for the production and decay of ClCOOH.

show abstract

A reduced dimension quantum reactive scattering study of OH + CO⇌H + CO2

Cited by 51 publications

References 12 publications

Resonances: Bridge between Spectroscopy and Dynamics

Resonances: Bridge between Spectroscopy and Dynamics

Combined Experimental–Theoretical Study of the OH + CO → H + CO₂ Reaction Dynamics

Infrared absorption of gaseous c-ClCOOH and t-ClCOOH recorded with a step-scan Fourier-transform spectrometer

Contact Info

Product

Resources

About

A reduced dimension quantum reactive scattering study of OH + CO⇌H + CO2

Cited by 51 publications

References 12 publications

Resonances: Bridge between Spectroscopy and Dynamics

Resonances: Bridge between Spectroscopy and Dynamics

Combined Experimental–Theoretical Study of the OH + CO → H + CO2 Reaction Dynamics

Infrared absorption of gaseous c-ClCOOH and t-ClCOOH recorded with a step-scan Fourier-transform spectrometer

Contact Info

Product

Resources

About

Combined Experimental–Theoretical Study of the OH + CO → H + CO₂ Reaction Dynamics