[CH2OH+, C2H4] and [C2H5+, CH2O] complexes

Tortajada, Jeanine; Audier, H. E.; Monteiro, C.; Mourgues, P.

doi:10.1002/oms.1210261020

Cited by 7 publications

(3 citation statements)

References 6 publications

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“…Over 100 papers have described the spectroscopic properties, − reaction mechanisms and kinetics, ,,,,,,,,,,,,,− …”

Section: Introductionmentioning

confidence: 99%

“…Over 100 papers have described the spectroscopic properties, reaction mechanisms and k i n e t i c s , 3 , 6 , 8 , 9 , 1 5 , 2 1 , 2 4 , 2 5 , 2 9 , 3 0 , 3 7 , 3 8 , 4 2 , 4 6 -8 7 thermochemistry, 10,17,18,45,47,50,59,[78][79][80]83,[88][89][90][91][92][93][94][95][96][97][98][99] and ab initio calculations 13,22,61,89,93,94,96,97, of the hydroxymethyl (CH 2 OH) radical and cation. These studies were motivated by the important roles that CH 2 OH and its isomer, CH 3 O, play in the combustion of hydrocarbon fuels, atmospheric pollution chemistry, surface science, and interstellar chemistry.…”

Section: Introductionmentioning

confidence: 99%

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Structural and Thermochemical Properties of Hydroxymethyl (CH₂OH) Radicals and Cations Derived from Observations of B̃²A‘(3p) ← X̃²A‘‘ Electronic Spectra and fromab InitioCalculations

1996

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B̃ 2A‘(3p) ← X̃ 2A‘‘ spectra of the isotopically substituted hydroxymethyl radicals (CH2OH, CH2OD, CD2OH, CD2OD) were observed between 39 700 and 43 000 cm-1 by 2+1, 2+2, and 1+1 resonance-enhanced multiphoton ionization (REMPI) spectroscopy. Analyses of the vibrational hot bands in these spectra show that the ν8 torsion modes and ν9 CH2-wag mode are strongly coupled and governed by nonharmonic potential energy functions; for example, for 12CH2 16OH(X̃ 2A‘‘) we obtain 2ν8 = 846 ± 6 cm-1(1σ), 1ν9 = 234 ± 5 cm-1, and 2ν9 = 615 ± 6 cm-1. Using MP2/6-311G(2df,2p) ab initio calculations, we constructed the two-dimensional potential energy surfaces that govern the ν8 torsion modes and ν9 CH2-wag in the X̃ 2A‘‘ radical and the X̃ 1A‘ cation core of the B̃ 2A‘(3p) Rydberg state. Energy levels calculated with these potential energy surfaces account for the REMPI bands originating from the ν8 hindered rotor and the ν9 CH2-wag modes. The experimental and ab initio results lead to improved heat capacities and entropies (S°298.15(CH2OH) = 244.170 ± 0.018 J (mol K)-1). Ab initio CBS-QCI/APNO calculations predict that Δf H°298.15(CH2OH) = −18.4 ± 1.3 kJ mol-1. Re-evaluation of photoionization data yields IPa(CH2OH) = 7.562 ± 0.004 eV. Re-evaluated photoionization appearance data, kinetic equilibrium data, and shock tube data indicate that Δf H°0(CH2OH+) = 718.1 ± 1.8 kJ mol-1, Δf H°298.15(CH2OH+) = 716.4 ± 1.8 kJ mol-1, Δf H°0(CH2OH) = −11.5 ± 1.3 kJ mol-1, and Δf H°298.15(CH2OH) = −17.8 ± 1.3 kJ mol-1. We report the proton affinity, PA0(CH2O) = 705.2 ± 1.9 kJ mol-1. Thermochemical tables based upon these values are presented for CH2OH and CH2OH+.

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“…Over 100 papers have described the spectroscopic properties, − reaction mechanisms and kinetics, ,,,,,,,,,,,,,− …”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Structural and Thermochemical Properties of Hydroxymethyl (CH₂OH) Radicals and Cations Derived from Observations of B̃²A‘(3p) ← X̃²A‘‘ Electronic Spectra and fromab InitioCalculations

1996

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“…indicated that significant amounts of 13 C-label exchange occurs during ethylene elimination from labeled analogues of 1 9 and 7 8b. However, later labeling experiments on 1 11 and 7 10 and ICR experiments on mixtures of [ 13 CH 2 OH] + and CH 2 CH 2 have failed to observe significant 13 C-label exchange. , …”

Section: Discussionmentioning

confidence: 99%

The Importance of Ion−Neutral Complexes in Gas-Phase Ionic Reactions: Fragmentation of [CH₃CH₂OCH₂]⁺ as a Prototypical Case

and

Radom

1998

J. Am. Chem. Soc.

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High level ab initio calculations performed at the G2 level have been used to characterize the potential energy surface for rearrangement and fragmentation of [CH3CH2OCH2]+. Ion−neutral complexes play a crucial role in the lowest-energy decomposition leading to elimination of water. RRKM calculations on the G2 surface are found to give results consistent with the experimentally observed metastable ion elimination products and with the results of various deuterium- and 13C-labeling experiments. The consequences of producing [CH3CH2OCH2]+ by isomerization from [CH3CHOCH3]+ and of producing [CH3CH2CHOH]+ by isomerization from [CH3C(OH)CH3]+ in relation to the rearrangement/fragmentation behavior are examined and found to be nicely consistent with experimental observations. Experimental thermochemical quantities such as rate-limiting barriers and heats of formation are found generally to be in good agreement with calculated values.

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Ion–neutral complexes in the unimolecular reactivity of organic cations in the gas phase

Longevialle

1992

Mass Spectrometry Reviews

255

119

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[CH₂OH⁺, C₂H₄] and [C₂H₅⁺, CH₂O] complexes

Abstract: Bowen et U Z . ' .~ have proposed that H-bonded complexes are CH3=CHC%+ + OH2 m/z 41 E+ 0 1 + CH3CH20CH2 2 4 Scheme 1

Cited by 7 publications

References 6 publications

Structural and Thermochemical Properties of Hydroxymethyl (CH₂OH) Radicals and Cations Derived from Observations of B̃²A‘(3p) ← X̃²A‘‘ Electronic Spectra and fromab InitioCalculations

Structural and Thermochemical Properties of Hydroxymethyl (CH₂OH) Radicals and Cations Derived from Observations of B̃²A‘(3p) ← X̃²A‘‘ Electronic Spectra and fromab InitioCalculations

The Importance of Ion−Neutral Complexes in Gas-Phase Ionic Reactions: Fragmentation of [CH₃CH₂OCH₂]⁺ as a Prototypical Case

Ion–neutral complexes in the unimolecular reactivity of organic cations in the gas phase

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[CH2OH+, C2H4] and [C2H5+, CH2O] complexes

Abstract: Bowen et U Z . ' .~ have proposed that H-bonded complexes are CH3=CHC%+ + OH2 m/z 41 E+ 0 1 + CH3CH20CH2 2 4 Scheme 1

Cited by 7 publications

References 6 publications

Structural and Thermochemical Properties of Hydroxymethyl (CH2OH) Radicals and Cations Derived from Observations of B̃2A‘(3p) ← X̃2A‘‘ Electronic Spectra and fromab InitioCalculations

Structural and Thermochemical Properties of Hydroxymethyl (CH2OH) Radicals and Cations Derived from Observations of B̃2A‘(3p) ← X̃2A‘‘ Electronic Spectra and fromab InitioCalculations

The Importance of Ion−Neutral Complexes in Gas-Phase Ionic Reactions: Fragmentation of [CH3CH2OCH2]+ as a Prototypical Case

Ion–neutral complexes in the unimolecular reactivity of organic cations in the gas phase

Contact Info

Product

Resources

About

[CH₂OH⁺, C₂H₄] and [C₂H₅⁺, CH₂O] complexes

Structural and Thermochemical Properties of Hydroxymethyl (CH₂OH) Radicals and Cations Derived from Observations of B̃²A‘(3p) ← X̃²A‘‘ Electronic Spectra and fromab InitioCalculations

Structural and Thermochemical Properties of Hydroxymethyl (CH₂OH) Radicals and Cations Derived from Observations of B̃²A‘(3p) ← X̃²A‘‘ Electronic Spectra and fromab InitioCalculations

The Importance of Ion−Neutral Complexes in Gas-Phase Ionic Reactions: Fragmentation of [CH₃CH₂OCH₂]⁺ as a Prototypical Case