Short-time kinetics of an irreversible bimolecular solution reaction: Asymptotic prediction by a non-Markovian Smoluchowski approach

• Wolfgang Naumann

  Interdisciplinary Group Time-Resolved Spectroscopy, University of Leipzig, Permoserstrasse 15, 04303 Leipzig, Germany

抄録

The effect of the nondiffusional short-time liquid dynamics on the kinetics of an irreversible bimolecular solution reaction (A+B→products) is investigated using a non-Markovian Smoluchowski approach. It is shown that due to the convolution-type basic equation in this concept, asymptotic rate coefficient predictions can be deduced from exact results of the Smoluchowski–Collins–Kimball theory. For the case that only the inertial effect plays a significant part in the nondiffusional reactant pair dynamics, an asymptotic short-time expansion of the rate coefficient was derived in this way. It explicitly indicates as a new reaction-kinetic result how the rate coefficient in the short-time region depends on the AB potential of mean force. Specified for the conditions of contact reactions in a simple hard-sphere fluid, the kinetic predictions of the new concept are compared with the results of other approaches.

収録刊行物

• The Journal of Chemical Physics

  The Journal of Chemical Physics 118 (20), 9297-9302, 2003-05-22

  AIP Publishing

キーワード

• Physical and Theoretical Chemistry
• General Physics and Astronomy

詳細情報

• CRID: 1362825893992644224
• NII論文ID: 30015687904
• DOI: 10.1063/1.1569472
• ISSN: 10897690
• ISSN: 00219606
• Web Site: https://pubs.aip.org/aip/jcp/article-pdf/118/20/9297/19294068/9297_1_online.pdf
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