Theoretical study of kinetic isotope effects on hydrogen abstraction reactions

• Autorzy: Kurosaki Y.
• Konferencja: Proceedings of the International Conference “2001 an Isotope Odyssey: New Application for a New Millenium", June 24-29, 2001, Zakopane, Poland
• Języki publikacji: EN

Abstrakty

EN

Effects of isotopic substitutions of "spectator" hydrogens on rate constants have been theoretically examined for the CH3 + H2 ' CH4 + H (I) and C2H + H2 ' C2H2 + H (II) reactions using variational transition state theory with the multidimensional semiclassical tunneling correction. A small but significant secondary isotope effect was found for reaction (I) but almost no isotope effect was found for reaction (II). This is because the potential energy surface for reaction (II) has an "early" character.

Słowa kluczowe

EN

ab initio molecular orbital method; hyrogen abstraction reaction; potential energy surface; secondary isotope effect; transition state theory; tunneling

• Wydawca: Institute of Nuclear Chemistry and Technology
• Czasopismo: Nukleonika
• Rocznik: 2002
• Tom: Vol. 47,suppl.1
• Strony: 81--88
• Opis fizyczny: Bibliogr. 3 poz., rys.

Twórcy

autor

Kurosaki Y.

• Advanced Photon Research Center, Japan Atomic Energy Research Institute, Umemidai, Kizu-cho, Soraku-gun, Kyoto 619-0215, Japan, Tel.: [phone], Fax: [phone],

Bibliografia

• 1. Kurosaki Y, Takayanagi T (1999) Theoretical study of an isotope effect on rate constans for CH3 + H2 → CH4 + H and CD3 + H2 → CD3H + H reactions using variational transition state theory and the multidimentional semiclassical tunneling method. J Chem Phys 110:10830–10842
• 2. Kurosaki Y, Takayanagi T (2000) Theoretical study of kinetic isotope effects on rate constants for the C2H + H2 → C2H2 + H reaction and its isotopic variants. J Chem Phys 113:4060–4072
• 3. Momose T, Hoshina H, Sogoshi N, Katsuki H, Wakabayashi T,Shida T (1998) Tunneling chemical reactions in solid parahydrogen: A case of CD3 + H2 → CD3H + H at 5 K. J Chem Phys 108:7334–7338