Thermal electron attachment rate to carbon tetrachloride, chloroform, dichloromethane, and sulfur hexafluoride

Ayala, J. A.; Wentworth, W. E.; Chen, E. C. M.

doi:10.1021/j150626a008

Cited by 49 publications

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“…Recently, an anion photoelectron spectra with an onset at about 2 eV and an E vd near 3.2 eV was analyzed using the literature AE a , 1.05(10) eV which implies E rr = 2.15 eV. [14][15][16][17][18][19][20][21][22][23][24][25][26][27] The theoretical E a (SF 6 ) also cover a wide range. 28 and MP2 aug-cc-pVDZ, 2.08 eV.…”

Section: Introductionmentioning

confidence: 99%

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THEORETICAL, EMPIRICAL AND EXPERIMENTAL ELECTRON AFFINITIES OF SF₆: SOLVING THE DENSITY FUNCTIONAL ENIGMA

Jalbout

León

Adamowicz

et al. 2007

J. Theor. Comput. Chem.

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We postulate that the adiabatic electron affinity of SF 6 is 2.40(10) eV, obtained from the photodetachment onset, 3.2(1) eV and a rearrangement energy of 0.8(1) eV. This eliminates the perceived "SF 6 density functional enigma". All of the experimental electron affinities are evaluated and 14 significantly different values selected to construct empirical anionic Morse potentials. These values are (in eV): 2.0.0(2). Comparisons are made to theoretical calculations and relative bond orders. The calculated electron affinities of SF 6 are: density functional, 1.6-3.0 eV; ab initio, −1.0-2.2 eV; semiempirical, 0.1-2.2 eV, and for SF 5 is 0.3-3.8 eV. Curves calculated using semiempirical, density functional and ab initio procedures are similar to the anionic Morse potentials. This work attempts to correct for differences in the EA calculated for this species.

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Section: Introductionmentioning

confidence: 99%

“…They reported values of 0.77 eV (KMLYP) to 2.81 eV (BLYP) with the aug-cc-pVQZ basis set. [15][16][17][18][19][20] While, the authors suggested MP2 aug-cc-pVTZ, G3, and CCSD(T) electron affinities we will explore the HIMPEC potentials.…”

Section: Introductionmentioning

confidence: 99%

THEORETICAL, EMPIRICAL AND EXPERIMENTAL ELECTRON AFFINITIES OF SF₆: SOLVING THE DENSITY FUNCTIONAL ENIGMA

Jalbout

León

Adamowicz

et al. 2007

J. Theor. Comput. Chem.

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“…In this case N,Nf-dicarbazyl (23) For personal use only. the following compounds: 3,9-di-(N-carbazy1)car-carbazole-CC1, system according to the following: bazole (24), N-cyano-3-(N-carbazy1)carbazole (26), and 3-(N-carbazy1)carbazole (27) in addition ['I C + hv + 'C* to products 1, 3, 22,28, and 29 (second column in [2] 'c* + cCI, -1(C~+.CCI,6-)*s,l, Table 1). [3] l(c6+ ~~.cC1,6-)*,,,, -[ c + ' c1-CCI,],,~, All the isolated and identified products, using ammonia after and during irradiation, support the carbazole radical cation transformation mechanism that we proposed in part I (15).…”

Section: Resultsmentioning

confidence: 99%

“…The excited states of aromatic molecules are therefore expected to be involved in charge transfer interactions with CCl, u 7 through exciplex formation. Low energy of the C-Cl bond in CCl, (21) and also the low activation energy of the dissociative process of electron attachment (22) promote the chemical activity of carbon tetrachloride. Therefore the electronic excitation of the electron donor molecule in the presence of CCl, is accompanied by the process of electron transfer to the CCl, molecule according to the scheme e-(donor) + CCI, + CC, + C1-which is the primary photochemical process initiating complex reactions.…”

Section: Introductionmentioning

confidence: 99%

One-electron photooxidation of carbazole in the presence of carbon tetrachloride. Part II. Carbon tetrachloride as a reaction medium. Use of ammonia after irradiation and during irradiation

Zelent¹,

Durocher²

1982

Can. J. Chem.

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BOGUMIL ZELENT and GILLES DUROCHER. Can. J. Chem. 60,2442Chem. 60, (1982.In part I of this series of papers we proposed the mechanism of electron transfer as the primary photochemical reaction in the carbazole -carbon tetrachloride system along with a secondary photochemical reaction initiated by transformations of the radical cation of carbazole in the solvent cage resulting in intermediates:CCI, H [ &I , ]@f@l, andIn this paper we discuss the influence of ammonia, used afier and during irradiation, on the mechanism of secondary transformation and the formation of thermodynamically stable products in the system studied. Such compounds as N-cyanocarbazole, I-cyanocarbazole, and 3-cyanocarbazole have been formed as the main products during neutralization of the photolyte solution by ammonia gas. The mechanism of formation of these compounds has been explained by the chemical reaction of ammonia with cations a and yi. If ammonia is present in the solution of carbazole in CCI, during irradiation, such products as N ,N1-dicarbazyl and N-cyanocarbazole are mainly formed along with 3-(N-carbazyl)carbazole, 3,9-di-(N-carbazyl)carbazole, and N-cyano-3-(N-carbazyI)carbazole. In such a case, reactions of radicals P are the determining factors in the secondary photochemical transformations. Radicals P are formed by the reaction involving ammonia with radical cations of carbazole. All the results in this paper have been discussed taking under consideration the influence of the reaction media o n the mechanism of photochemical transformation of carbazole.BOGUMIL ZELENT et GILLES DUROCHER. Can. J. Chem. 60, 2442Chem. 60, (1982.Dans la premiere partie de cette sCrie d'articles nous avons suggerk que le mdcanisme photochimique primaire lors de la reaction du carbazole et du tetrachlorure de carbone en etait un de transfert Clectronique. La reaction photochimique secondaire consiste e n la transformation du radical cation du carbazole dans la cage du solvant pour donner les intermediaires suivants:Dans cet article, nous discuterons de l'influence de l'ammoniac utilise apres et avant l'irradiation, sur le mCcanisme secondaire d e transformation et de formation de photoproduits thermodynamiquement stables. Lorsque I'ammoniac est ajoute apres l'irradiation, le cyano-N carbazole, le cyano-l carbazole et le cyano-3 carbazole ont ttC surtout obtenus. Ce resultat s'explique par la rdaction d e I'ammoniac avec les cations a et y,. Si au contraire, l'ammoniac est present dans la solution du carbazole dans le CC1, au cours d e l'irradiation, les produits suivants sont obtenus avec un bon rendement: dicarbazyl-N,N' et cyano-N carbazole. Les produits suivants sont Bgalement obtenus: (carbazyl-N)-3 carbazole, di-(carbazyl-N)-3.9 carbazole et cyano-N(carbazy1-N)-3 carbazole.Les radicaux p sont alors impliquks dans la transformation photochimique. Ces radicaux P sont produits suite a la rdaction de l'ammoniac avec les radicaux cations du carbazole. Tous les resultats sont discut6s en tenant compte de I'influence du milieu riactionnel sur le...

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“…The electronic excitation of donor molecules like aromatic amines, which possess comparatively low ionization potential in the presence of CCl,, leads to electron transfer in the transiently formed exciplex (7,(33)(34)(35). This is accomSuch chemical activity in CC1, is connected not only with its significant electron affinity (2.12 eV) (28) but also with its comparatively low C-C1 bonding energy (231.2 kJ mol-') (36) and the low (-0) activation energy of the dissociative process for the electron attachment (37). Because of its properties, CCl, is frequently used as an active component in photochemical reactions.…”

Section: Introductionmentioning

confidence: 99%

One-electron photooxidation of N-ethylcarbazole in the presence of carbon tetrachloride. Products and mechanism of the photochemical reaction

Zelent¹,

Durocher²

1985

Can. J. Chem.

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This paper is dedicated to Professor Camille Sandorfjr on the occasion of his 65th birthdayBOGUMIL ZELENT and GILLES DUROCHER. Can. J. Chem. 63, 1654 (1985.The mechanism of the photodecomposition of N-ethylcarbazole (NEC) in the presence of carbon tetrachloride has been discussed on the basis of the photoproducts identified. The photodissociation of the N-ethyl bond and the electron transfer in the transiently formed ex-CT complex, '(NEC"..-CCI.,'-)*, have been proposed as the primary photochemical processes involved irr the singlet excited NEC molecule. The latter, treated as the main process, leads to the radical cation of NEC, chloride ion, and trichloromethyl radical in the solvent cage, [NEC"CI-CCI,]. The other reactions in the system studied are analysed following the decomposition of NEC" in the presence of C1-and CCI,, which can occur by the N-ethyl group and (or) by the aromatic ring. The formation of intermediate products such as in the solvent cage gives rise to secondary photochemical reactions in the system studied. The polarity and chemical activity of the reaction media used strongly influence the nature of the secondary photochemical transformations both in and outside the solvent cage. The formation mechanism of the photochemical reaction products in CCI, when ammonia was used, after and during irradiation, has been explained mainly by the transformations of the radical a, and cation a~. as well as by the carbazyl radical P, which is also formed in the reaction medium. On the other hand, reaction of the cation y: explains the formation of the photoproducts in the irradiated solution of NEC with CClj in ethanol. These photochemical results have been compared to the photochemical reactions involved in the carbazole-CC14 system. BOGUMIL ZELENT et GILLES DUROCHER. Can. J. Chem. 63, 1654 (1985).Le mCcanisme de la photodCcomposition du Cthyl-N-carbazole (NEC) en prksence de tktrachlorure de carbone (CCI,) est analysC suite ['identification des photoproduits obtenus. La photodissociation du lien N-Cthyl ainsi que le transfert Clectronique dans le complexe excitC de transfer de charge '(NEC''...CCI,'-)* peuvent Ctre la cause de l'acte photochimique primaire suite a I'excitation du NEC dans son Ctat premier singulet. Le phototransfert Clectronique conduit I'apparition du radical cation du NEC, a I'anion chlorure et au radical trichloromCthyl dans la cage du solvant, [NECt'CI-CCI,]. La dCcomposition du radical cation en prksence de C 1 et de CCI, s'effectue par I'attaque du groupe N-Cthyl ou par le noyau aromatique. Les produits intermkdiaires suivants: dans la cage du solvant donnent lieu a ]'ensemble des rCactions photochimiques secondaires. La polarit6 ainsi que I'activitC chimique du milieu rkactionnel influencent fortement la nature des transformations photochimiques secondaires dans la cage du solvant et en dehors de celle-ci. Le mecanisme de formation des produits photochimiques dans le CCI, lorsque I'ammoniaque est ajoutC au cours et aprks I'irradiation s'explique principalement par la transformat...

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Thermal electron attachment rate to carbon tetrachloride, chloroform, dichloromethane, and sulfur hexafluoride

Cited by 49 publications

References 0 publications

THEORETICAL, EMPIRICAL AND EXPERIMENTAL ELECTRON AFFINITIES OF SF₆: SOLVING THE DENSITY FUNCTIONAL ENIGMA

THEORETICAL, EMPIRICAL AND EXPERIMENTAL ELECTRON AFFINITIES OF SF₆: SOLVING THE DENSITY FUNCTIONAL ENIGMA

One-electron photooxidation of carbazole in the presence of carbon tetrachloride. Part II. Carbon tetrachloride as a reaction medium. Use of ammonia after irradiation and during irradiation

One-electron photooxidation of N-ethylcarbazole in the presence of carbon tetrachloride. Products and mechanism of the photochemical reaction

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Thermal electron attachment rate to carbon tetrachloride, chloroform, dichloromethane, and sulfur hexafluoride

Cited by 49 publications

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THEORETICAL, EMPIRICAL AND EXPERIMENTAL ELECTRON AFFINITIES OF SF6: SOLVING THE DENSITY FUNCTIONAL ENIGMA

THEORETICAL, EMPIRICAL AND EXPERIMENTAL ELECTRON AFFINITIES OF SF6: SOLVING THE DENSITY FUNCTIONAL ENIGMA

One-electron photooxidation of carbazole in the presence of carbon tetrachloride. Part II. Carbon tetrachloride as a reaction medium. Use of ammonia after irradiation and during irradiation

One-electron photooxidation of N-ethylcarbazole in the presence of carbon tetrachloride. Products and mechanism of the photochemical reaction

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THEORETICAL, EMPIRICAL AND EXPERIMENTAL ELECTRON AFFINITIES OF SF₆: SOLVING THE DENSITY FUNCTIONAL ENIGMA

THEORETICAL, EMPIRICAL AND EXPERIMENTAL ELECTRON AFFINITIES OF SF₆: SOLVING THE DENSITY FUNCTIONAL ENIGMA