An experimental determination of the geometry and electron affinity of methyl radical

Ellison, G. Barney; Engelking, P. C.; Lineberger, W. C.

doi:10.1021/ja00476a054

Cited by 226 publications

(100 citation statements)

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“…However, they correlate well with the experimental enthalpy of the X + H À reaction (533 kJ/mol [33], 396 kJ/mol [34], 389 kJ/mol [35], for O, CH 2 , and NH, respectively) that may roughly simulate the transfer of two 5s electrons from the metal to an adsorbate.…”

Section: O Nh and Ch 2 Adsorbatessupporting

confidence: 72%

Trends in adsorption of open-shell atoms and small molecular fragments on the Ag(111) surface

2006

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Section: O Nh and Ch 2 Adsorbatessupporting

confidence: 72%

Trends in adsorption of open-shell atoms and small molecular fragments on the Ag(111) surface

2006

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“…The photoelectron spectrum of this anion was completely inconsistent with the known photoelectron spectra of the other anionic possibilities at this mass, NH − or CHD − . However, the observed photoelectron spectrum was consistent with the one expected for the methide anion, which is dominated by an extended progression in the umbrella vibrational mode of the methyl radical (40). Fortunately, analysis of the photoelectron spectrum of such a simple molecule does not require a full understanding of the synthetic procedures leading to its formation!…”

Section: Wwwannualreviewsorg • Once Upon Anion: a Tale Of Photodetasupporting

confidence: 69%

Once upon Anion: A Tale of Photodetachment

Lineberger

2013

Annu. Rev. Phys. Chem.

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This contribution is very much a personal history of a journey through the wonderful world of anion chemistry, and a tale of how advances in laser technologies, theoretical methods, and computational capabilities continuously enabled advances in our understanding. It is a story of the excitement and joy that come from the opportunity to add to the fabric of science, and to do so by working as a group of excited explorers with common goals. The participants in this journey include me, my students and postdoctoral associates, my collaborators, and our many generous colleagues. It all happened, in the words of the Beatles, "with a little help from my friends." Actually, it was so much more than a little help!

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“…Indeed DePuy and co-workers (34) have estimated a gas-phase acidity for C2H6 of 761 kJ mol-' , which leads to an electron affinity of -37.7 W mol-' for C2H5. For comparison, the electron affinity of CH3 is 7.5 kJ mol-' (35). Using the AH" acid for C2H6, the enthalpy of the hypothetical roducts P [C2H5-+ CH3CHO] is calculated to be -234 kJ mol-relative to the s-butoxide ion; thus, assuming equal ion-dipole stabiliza- The same arguments apply for the 3-pentoxide ion (entry 14, Table 1) where C2H6 elimination is of only minor importance relative to H2 elimination over the entire collision energy regime (Fig.…”

Section: A-h Ah:(ah)" a C I D (~~L B Ah;(a-) H-h Ch3-h C2h5-h (Ch3)2cmentioning

confidence: 99%

Fragmentation of alkoxide ions following collisional activation. An energy-resolved study

Mercer¹,

Harrison²

1988

Can. J. Chem.

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. Can. J. Chem. 66, 2947Chem. 66, (1988.The collisionally activated dissociation reactions of the C2 to C5 alkoxide ions have been studied for collisons occurring at 8 keV kinetic energy and also over the range 5 to 100 eV kinetic energy. The alkoxide ions fragment by 1,2-elimination of H2 andlor an alkane. Thus, primary alkoxide ions fragment by elimination of H, only, secondary alkoxide ions show elimination of Hz and alkane molecules, while tertiary alkoxide ions show elimination of alkanes only. In alkane elimination, loss of CH4 is much more facilie than loss of larger alkanes. For secondary alkoxide ions, where more than one elimination reaction occurs, the energy dependence of fragmentation has been explored over the collision energy range 5 to 100 eV. The results are interpreted in terms of a step-wise mechanism involving formation of an anion-carbonyl compound ion-dipole complex, followed by proton abstraction by the H-or alkyl anion leading to the final products. The relative importance of the reaction channels is determined by the relative stabilities of these ion-dipole complexes. ROGER S. MERCER et ALEX G. HARRISON. Can. J. Chem. 66,2947 (1988.On a CtudiCe les reactions de dissociation des ions alcoolates C2 a CS activkes par des collisions se produisant i une Cnergie cinktique de 8 keV ainsi qu'i des energies cinetiques allant de 5 a 100 eV. Les ions alcoolates se fragmentent par une elimination-l,2 de Hz eVou d'alcane. Ainsi, les ions alcoolates primaires se fragmentent uniquement par une elimination de Hz; par ailleurs, les ions alcoolates secondaires presentent de l'elimination de H2 ainsi que celle de molecules d'alcanes alors que les ions alcoolates tertiaires ne presentent que de l'elimination d'alcanes. Lors de l'elimination d'alcanes, la perte de CH4 est beaucoup plus facile que celle des alcanes plus volumineux. Dans le cas des alcoolates secondaires oh il se produit plus d'une elimination, on a CvaluC la relation qui existe entre I'energie de collision (de 5 100 eV) et le type de fragmentation. On interprete les resultats en fonction d'un mecanisme par Ctape impliquant la formation d'un complexe ion-dip6le d'un compose anioncarbonyle, suivie par l'enlevernent d'un proton par un H-ou par un anion alkyle, conduisant aux produits. On a determine l'importance relative des diverses voies rtactionnelles en se basant sur les stabilites relatives de ces complexes ion-dip6les.[Traduit par la revue] Introduction Studies of the fragmentation of gaseous ions have long been invaluable sources of information concerning the structures and chemistry of such species (1, 2). This information is even more useful if the internal energy of the fragmenting ions is known and can be varied in a controlled fashion; such energy-resolved studies permit the establishment of break-down graphs expressing the variation of fragment ion yields with internal energy. Energy-resolved data for odd-electron molecular cations can be obtained with high precision by photoelectron/photoion coincidence (PEPICO) experiments (3-5)...

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An experimental determination of the geometry and electron affinity of methyl radical

Cited by 226 publications

References 1 publication

Trends in adsorption of open-shell atoms and small molecular fragments on the Ag(111) surface

Trends in adsorption of open-shell atoms and small molecular fragments on the Ag(111) surface

Once upon Anion: A Tale of Photodetachment

Fragmentation of alkoxide ions following collisional activation. An energy-resolved study

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