Density functional and G2 study of the strength of the OH bond in CF3OH

Segovia, Marc E.; Ventura, Oscar N.

doi:10.1016/s0009-2614(97)00860-9

Cited by 14 publications

(10 citation statements)

References 31 publications

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“…Previous studies have shown that different methods of DFT can also reproduce experimental proton affinities of simple anions with remarkable accuracy . Our initial attempts at the B3P86 level revealed that very good agreement could be achieved with the experimental proton affinity of GeH 3 - (see below), but not with the reported electron affinity of ·GeH 3 .…”

Section: Resultsmentioning

confidence: 69%

Calculation of the Proton and Electron Affinity of Simple Ge-Containing Species Using Density Functional Theory

Morgon

Riveros

1998

J. Phys. Chem. A

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Basis sets developed using the generator coordinate method and a pseudopotential have been adapted to density functional theory to calculate the proton affinity of GeH4, GeH3-, GeF3 -, CH3GeH2 -, and Ge(OH)3 - and the electron affinity of ·GeH3 and ·GeF3. The proton affinity of GeH4 is calculated to be 673.9 kJ mol-1 at 298 K, while values for GeH3 - (1505.0 kJ mol-1) and CH3GeH2 - (1529.0 kJ mol-1) are in excellent agreement with experimental values. The electron affinity of ·GeF3 is predicted to be in the range of 3.5−3.7 eV by calculations using different functionals and ab initio methods. The present calculations reveal that the B3P86 method can yield proton affinities comparable to those obtained with other high-quality methods but consistently overestimates electron affinities of simple Ge radicals.

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Section: Resultsmentioning

confidence: 69%

Calculation of the Proton and Electron Affinity of Simple Ge-Containing Species Using Density Functional Theory

Morgon

Riveros

1998

J. Phys. Chem. A

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“…Thus, we can have an independent theoretical assessment of Δ f H ° 298K (HSO) to compare with the ab initio results already present in the literature. We have shown previously 33–39 that density functional methods using large basis sets and isodesmic reactions can produce very accurate thermochemical results, bettering G2 and even coupled cluster singles and doubles calculations with perturbative inclusion at triple excitation [CCSD(T)] methods in many cases. We expect that the results obtained for HSO employing this methodology will be of the same quality as those obtained before.…”

Section: Introductionmentioning

confidence: 99%

Density functional investigation of atmospheric sulfur chemistry. I. Enthalpy of formation of HSO and related molecules

Denis

Ventura

2000

Int. J. Quantum Chem.

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The enthalpy of formation of several species intervening in the atmospheric chemistry of sulfur compounds (SH, H2S, SO, HSO, SOH) have been calculated using density functional theory with correlation consistent basis sets and extrapolation to the complete basis set limit. Excellent agreement with experiment is found for the species of which the enthalpy of formation are well determined. The values predicted for HSO [ΔfH°298K(HSO)=−27.8±2.1 kJ/mol] and SOH [ΔfH°298K(SOH)=−6.8±2.1 kJ/mol] agree well with previous multireference configuration interaction (MR‐CI) calculations. Based on these results, it is determined that the reaction of HSO with ozone is endothermic at all temperatures but spontaneous above 220 K because of entropic effects. Both the reactions of dissociation SOH→H+SO and isomerization HSO→SOH are studied in detail, and the transition states located. The results are also in agreement with the much more costly MR‐CI results. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 80: 439–453, 2000

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“…To understand the fate of this species, the thermochemistry of the processes in which it may participate needs to be determined and explained. Various theoretical and experimental studies have produced values for the oxygen−hydrogen bond dissociation enthalpy, BDE(O−H), in trifluoromethanol (CF 3 O−H) ranging from 110 to 124 kcal mol -1 . Now, if one accepts that the BDE is comparable to that in water, that is, the BDE(O−H) in CF 3 O−H is about 119 kcal mol -1 , then on the basis of a reaction enthalpy assessment a similar reactivity for CF 3 O • relative to HO • may be anticipated in hydrogen atom abstraction reactions.…”

Section: Introductionmentioning

confidence: 99%

O−O Bond Dissociation Enthalpy in Di(trifluoromethyl) Peroxide (CF₃OOCF₃) as Determined by Very Low Pressure Pyrolysis. Density Functional Theory Computations on O−O and O−H Bonds in (Fluorinated) Derivatives

et al. 2000

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The thermal decomposition of di(trifluoromethyl) peroxide (between 575 and 900 K) and di-tert-butyl peroxide (between 425 and 650 K) has been investigated by means of a very low pressure pyrolysis method. The Arrhenius equations for homolytic oxygen−oxygen bond rupture obey log(k 1/s-1) = 15.30−45.0 kcal mol-1/2.303RT for CF3O−OCF3 and log(k 2/s-1) = 15.30−37.4 kcal mol-1/2.303RT for Me3CO−OCMe3. The oxygen−oxygen bond dissociation enthalpies, BDE(O−O), at 298 K for the peroxides are derived to be 47.5 ± 0.5 (CF3O−OCF3) and 38.9 ± 0.5 kcal mol-1 (Me3CO−OCMe3). Various density functional theory calculations have been utilized to compute the BDEs for XO−H, XO−OH, and XO−OX, with X = H, CF3, and Me3C. Expansion of the basis set and the application of the restricted open-shell (RO) formalism for the radical species affords better agreement with experimental values. Using isodesmic reactions, a convergence is obtained for the BDE(O−H) in trifluoromethanol (CF3O−H) toward 118.8 ± 0.5 kcal mol-1. Reevaluation of literature thermokinetic data leads to BDE(F−CF2O•) of 27 ± 1, and BDE(CF3O−F) of 48 ± 1 kcal mol-1.

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Density functional and G2 study of the strength of the OH bond in CF3OH

Cited by 14 publications

References 31 publications

Calculation of the Proton and Electron Affinity of Simple Ge-Containing Species Using Density Functional Theory

Calculation of the Proton and Electron Affinity of Simple Ge-Containing Species Using Density Functional Theory

Density functional investigation of atmospheric sulfur chemistry. I. Enthalpy of formation of HSO and related molecules

O−O Bond Dissociation Enthalpy in Di(trifluoromethyl) Peroxide (CF₃OOCF₃) as Determined by Very Low Pressure Pyrolysis. Density Functional Theory Computations on O−O and O−H Bonds in (Fluorinated) Derivatives

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Density functional and G2 study of the strength of the OH bond in CF3OH

Cited by 14 publications

References 31 publications

Calculation of the Proton and Electron Affinity of Simple Ge-Containing Species Using Density Functional Theory

Calculation of the Proton and Electron Affinity of Simple Ge-Containing Species Using Density Functional Theory

Density functional investigation of atmospheric sulfur chemistry. I. Enthalpy of formation of HSO and related molecules

O−O Bond Dissociation Enthalpy in Di(trifluoromethyl) Peroxide (CF3OOCF3) as Determined by Very Low Pressure Pyrolysis. Density Functional Theory Computations on O−O and O−H Bonds in (Fluorinated) Derivatives

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O−O Bond Dissociation Enthalpy in Di(trifluoromethyl) Peroxide (CF₃OOCF₃) as Determined by Very Low Pressure Pyrolysis. Density Functional Theory Computations on O−O and O−H Bonds in (Fluorinated) Derivatives