Effects of Electron Correlation and Scalar Relativistic Corrections on the Thermochemical and Spectroscopic Properties of HOF

Ramachandran, B.; Vegesna, Naga Srivani; Peterson, Kirk A.

doi:10.1021/jp035266h

Cited by 13 publications

(22 citation statements)

References 62 publications

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“…[82]. These results are also very close to those obtained by Ramachandran et al [77] using a AVTZ basis set and a CCSD(T) method: 3746, 1390 and 915 cm −1 . Also, this PES has been used recently for describing the O( 1 D)+HF reactive collision leading to results in rather good agreement with the currently available experimental data [83].…”

Section: Topological Characteristicssupporting

confidence: 90%

Transition state spectroscopy of open shell systems: Angle-resolved photodetachment spectra for the adiabatic singlet states of OHF

Gómez-Carrasco

Aguado

Paniagua

et al. 2007

Journal of Photochemistry and Photobiology A: Chemistry

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In this work three-dimensional potential energy surfaces of the first five singlet states of OHF are developed based on fits of more than 10000 highly accurate ab initio points. An approximate treatment is presented for the calculation of the anisotropy parameter describing the electron angular distribution photodetached from a molecular anion. This method is used to calculate the angle-resolved photoelectron spectra in the photodetachment of OHF −. The wave packet formed in the neutral OHF system is placed at the transition state region, and yields the formation of OH+F and HF+O products. The results are compared with the recent experimental measurements published by Neumark(Phys. Chem. Chem. Phys. 7, 433 (2005)). The intensity found at low electron kinetic energy including these 5 states and the three lower triplet states is found to be low. To analyze the effect of higher electronic states more excited 1 Σ − , 3 Σ + and 3 ∆ states are calculated at collinear geometry. The agreement with the experimental data improves, thus demonstrating that the correct simulation of the photodetachment spectrum at 213 nm involves at least 12 electronic states. All the structures of the experimental spectra are semiquantitatively reproduced finding an overall good agreement. It is concluded that the main problem of the simulation is in the intensity and anisotropy parameters. An alternative to their calculation would be to fit their values to reproduce the experimental results, but this would require to separate the contribution arising from different final electronic states.

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Section: Topological Characteristicssupporting

confidence: 90%

Transition state spectroscopy of open shell systems: Angle-resolved photodetachment spectra for the adiabatic singlet states of OHF

Gómez-Carrasco

Aguado

Paniagua

et al. 2007

Journal of Photochemistry and Photobiology A: Chemistry

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“…The dissociation energies D 0 's of the three molecules are smaller than the experimental ones by about 0.2 eV. However, the agreement improves as the AVnZ basis set grows, 24 finally reaching a good accord with the experiment, specially for OH and HF.…”

Section: Ab Initio Calculations and Fit Of The Surfacementioning

confidence: 54%

Direct versus resonances mediated F+OH collisions on a new A″3 potential energy surface

Gómez-Carrasco

González-Sánchez

Aguado

et al. 2004

The Journal of Chemical Physics

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A theoretical study of the F(2P) + OH(2Pi) --> HF(1Sigma+) + O(3P) reactive collisions is carried out on a new global potential energy surface (PES) of the ground 3A" adiabatic electronic state. The ab initio calculations are based on multireference configuration interaction calculations, using the aug-cc-pVTZ extended basis sets of Dunning et al. A functional representation of the PES shows no nominal barrier to reaction, contrary to previous results by others. Wave packet and quasiclassical trajectory calculations have been performed for this PES to study the F + OH(v = 0,j) reactive collision. The comparison was performed at fixed and constant values of the total angular momentum from 0 to 110 and relative translational energy up to 0.8 eV. The reaction presents a dynamical barrier, essentially due to the zero-point energy for the bending vibration near the saddle point. This determines two different reaction mechanisms. At energies higher than approximately 0.125 eV the reaction is direct, while below that value it is indirect and mediated by heavy-light-heavy resonances. Such resonances, also found in the simulations of the photodetachment spectrum of the triatomic anion, manifest themselves in the quasiclassical simulations, too, where they are associated to periodic orbits.

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“…Experimental uncertainties are ± 1σ. b Large basis set CCSD(T)+core-valence+scalar relativistic corrections, ref . c Reference 57. d Reference 78. e CCSD(T)/cc-pVTZ, ref .…”

Section: Resultsmentioning

confidence: 99%

Rozen's Epoxidation Reagent, CH₃CN·HOF: A Theoretical Study of Its Structure, Vibrational Spectroscopy, and Reaction Mechanism

Sertchook

Boese²,

Martin

2005

J. Phys. Chem. A

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Rozen's epoxidation reagent, CH(3)CN.HOF, and a prototype epoxidation reaction employing it, have been subjected to an extensive ab initio and density functional study. Its anharmonic force field reveals a very strong red shift for the OH stretch and a strong blue shift for the HOF bend, in semiquantitative agreement with experiment. The very strong hydrogen bond (8.20 kcal/mol at the W1 level) not only serves to stabilize the reactant but also considerably lowers the barrier height for epoxidation of ethylene. Moreover, the reaction byproduct HF is found to act autocatalytically. The OH moiety acquires HO(+) character in the transition state. Our W1 benchmark data for the reaction profile allow the performance of various DFT functionals to be assessed. In general, "kinetics" functionals overestimate barrier heights, the BMK functional less so than the others. The B1B95 and TPSS33B95 meta-GGA functionals both perform very well, whereas general-purpose hybrid GGAs underestimate barrier heights. The simple PBE0 functional does reasonably well.

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Effects of Electron Correlation and Scalar Relativistic Corrections on the Thermochemical and Spectroscopic Properties of HOF

Cited by 13 publications

References 62 publications

Transition state spectroscopy of open shell systems: Angle-resolved photodetachment spectra for the adiabatic singlet states of OHF

Transition state spectroscopy of open shell systems: Angle-resolved photodetachment spectra for the adiabatic singlet states of OHF

Direct versus resonances mediated F+OH collisions on a new A″3 potential energy surface

Rozen's Epoxidation Reagent, CH₃CN·HOF: A Theoretical Study of Its Structure, Vibrational Spectroscopy, and Reaction Mechanism

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Effects of Electron Correlation and Scalar Relativistic Corrections on the Thermochemical and Spectroscopic Properties of HOF

Cited by 13 publications

References 62 publications

Transition state spectroscopy of open shell systems: Angle-resolved photodetachment spectra for the adiabatic singlet states of OHF

Transition state spectroscopy of open shell systems: Angle-resolved photodetachment spectra for the adiabatic singlet states of OHF

Direct versus resonances mediated F+OH collisions on a new A″3 potential energy surface

Rozen's Epoxidation Reagent, CH3CN·HOF: A Theoretical Study of Its Structure, Vibrational Spectroscopy, and Reaction Mechanism

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Product

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Rozen's Epoxidation Reagent, CH₃CN·HOF: A Theoretical Study of Its Structure, Vibrational Spectroscopy, and Reaction Mechanism