caa a22 4500 465818730 CHVBK 20180323112129.0 cr unu---uuuuu 170327e19900301xx s 000 0 eng 10.1007/BF01114534 doi (NATIONALLICENCE)springer-10.1007/BF01114534 Multi-exponential unimolecular rate formulae [Elektronische Daten] [S. Vatsya, H. Pritchard] Summary: We derive analytic expressions for the upper and lower bounds to the rate constant of a unimolecular reaction, which is treated as a competition between decay of reactive states and an arbitrary number of collisional relaxation processes all with different rate constants. The unimolecular rate is identified with the eigenvalue of smallest numerical magnitude. An analytic approximation to the corresponding eigenvector is also derived. Behaviour of the low-pressure rate constant is investigated and an analytic expression, in terms of the populations and the rates connecting them, is derived for the collision efficiency parameter β c . It is shown that there is a direct relationship between the limiting low-pressure rate and the reactive fraction of molecules only in the special case where all unreactive molecules are connected by a pure exponential collisional relaxation. Springer-Verlag, 1990 Unimolecular fall-off nationallicence Multi-exponential decay nationallicence Collision efficiency nationallicence Vatsya S. Centre for Research in Earth and Space Science, York University, M3J 1P3, Downsview, Ontario, Canada aut Pritchard H. Centre for Research in Earth and Space Science, York University, M3J 1P3, Downsview, Ontario, Canada aut Theoretica chimica acta Springer-Verlag 77/2(1990-03-01), 63-84 0040-5744 77:2<63 1990 77 214 https://doi.org/10.1007/BF01114534 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF01114534 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Vatsya S. Centre for Research in Earth and Space Science, York University, M3J 1P3, Downsview, Ontario, Canada aut NATIONALLICENCE 700 1- Pritchard H. Centre for Research in Earth and Space Science, York University, M3J 1P3, Downsview, Ontario, Canada aut NATIONALLICENCE 773 0- Theoretica chimica acta Springer-Verlag 77/2(1990-03-01), 63-84 0040-5744 77:2<63 1990 77 214 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer