A Direct ab Initio Trajectory Study on the Gas-Phase SN2 Reaction OH- + CH3Cl → CH3OH + Cl

Autor:	Hiroto Tachikawa, Manabu Igarashi, Teruo Ishibashi
Rok vydání:	2002
Předmět:	Chemistry Ab initio quantum chemistry methods Potential energy surface Degrees of freedom (physics and chemistry) Ab initio SN2 reaction Molecular orbital Physical and Theoretical Chemistry Atomic physics Trajectory (fluid mechanics) Molecular physics Basis set
Zdroj:	The Journal of Physical Chemistry A. 106:10977-10984
ISSN:	1520-5215 1089-5639
Popis:	Direct ab initio trajectory calculations have been applied to a SN2 reaction, OH- + CH3Cl → CH3OH + Cl-. First, static ab initio molecular orbital (MO) calculations with several basis sets were examined to select the most convenient and best fit basis set to that of high-quality calculations. As a result of the static ab initio calculations, it was found that the Hartree−Fock (HF)/3-21+G(d) calculation reasonably represents a potential energy surface calculated at the MP2/6-311++G(2df,2pd) level. Next, direct ab initio dynamics calculations using the 3-21+G(d) basis set were carried out for the SN2 reaction. A full dimensional potential energy surface including all degrees of freedom was used in the dynamics calculation. The collision energies chosen were Ecoll = 5 and 25 kcal/mol. In the collisions at Ecoll = 5 and 25 kcal/mol, 48% and 63% of the total available energies were, respectively, partitioned into the relative translational mode between CH3OH and Cl-. Also, it was predicted that the C−H stretch...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::29a5ef22ff262e79bee9366d40c43964 https://doi.org/10.1021/jp0210632 Zobrazit plný text záznamu