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Titolo:
The mechanism of the reaction FH+H2C=CH2 -> H3C-CFH2. Investigation of hidden intermediates with the unified reaction valley approach
Autore:
Cremer, D; Wu, AA; Kraka, E;
Indirizzi:
Univ Gothenburg, Dept Theoret Chem, S-41320 Gothenburg, Sweden Univ Gothenburg Gothenburg Sweden S-41320 em, S-41320 Gothenburg, Sweden
Titolo Testata:
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
fascicolo: 5, volume: 3, anno: 2001,
pagine: 674 - 687
SICI:
1463-9076(2001)3:5<674:TMOTRF>2.0.ZU;2-E
Fonte:
ISI
Lingua:
ENG
Soggetto:
ANALYZING VIBRATIONAL-SPECTRA; POTENTIAL-ENERGY CHARACTERISTICS; AB-INITIO CALCULATIONS; GAS-PHASE ADDITION; CHEMICAL-REACTIONS; REACTION-PATH; MOLECULAR-STRUCTURE; HYDROGEN-FLUORIDE; CATALYTIC ACTION; ABINITIO MO;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
81
Recensione:
Indirizzi per estratti:
Indirizzo: Cremer, D Univ Gothenburg, Dept Theoret Chem, Reutersgatan 2, S-41320 Gothenburg, Sweden Univ Gothenburg Reutersgatan 2 Gothenburg Sweden S-41320 Sweden
Citazione:
D. Cremer et al., "The mechanism of the reaction FH+H2C=CH2 -> H3C-CFH2. Investigation of hidden intermediates with the unified reaction valley approach", PHYS CHEM P, 3(5), 2001, pp. 674-687

Abstract

The unified reaction valley approach (URVA) is used to investigate the mechanism of the reaction H2C=CH2 + FH --> H3C-CH2F (reaction I) at different levels of theory (HF, MP2 and CCSD(T)) with different basis sets (6-31G(d,p), 6-311 + +G(3df,3dp) and cc-pVTZ). URVA is based on the reaction path Hamiltonian, the intrinsic reaction coordinate, and the characterization of normal modes, reaction path vector and curvature vector in terms of generalized adiabatic modes associated with internal parameters that are used to describe the reaction complex. In addition, URVA combines the investigation ofthe harmonic reaction valley with the analysis of attractive and repulsiveforces exerted on the nuclei by analyzing the changes of the electron density distribution along the reaction path. It is shown that reaction I involves two different chemical processes: (a) the simultaneous FH bond cleavageand CH bond formation leading to an intermediate structure with ion-pair character and (b) the formation of a CF bond and, by this, the final product. The properties of the reaction complex suggest the possibility that a hidden intermediate formed in process (a), which upon a change in the reactionconditions (environment, substitution pattern) can convert into a real intermediate (in solution: solvated ion pairs). Using the results of the URVA analysis of reaction I predictions with regard to the occurrence of hidden intermediates in related addition/cycloaddition reactions are made.

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Documento generato il 07/04/20 alle ore 23:12:39