From owner-chemistry@ccl.net Sun Mar 27 12:42:01 2011
From: "Jim Kress ccl_nospam * kressworks.com" <owner-chemistry .. server.ccl.net>
To: CCL
Subject: CCL: Pressure dependence in reaction rate kinetics calculations
Message-Id: <-44228-110327123933-4593-EIkz6b1vTx6xnTkLNDD5Pw .. server.ccl.net>
X-Original-From: "Jim Kress" <ccl_nospam^-^kressworks.com>
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Date: Sun, 27 Mar 2011 12:39:07 -0400
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Sent to CCL by: "Jim Kress" [ccl_nospam/a\kressworks.com]
The link you gave should be:

http://www.frad.t.u-tokyo.ac.jp/~miyoshi/ssumes/

Jim

> -----Original Message-----
> From: owner-chemistry+ccl_nospam==kressworks.com%x%ccl.net [mailto:owner-
> chemistry+ccl_nospam==kressworks.com%x%ccl.net] On Behalf Of Ted Dibble
> tsdibble]_[syr.edu
> Sent: Wednesday, March 23, 2011 11:29 AM
> To: Kress, Jim 
> Subject: CCL: Pressure dependence in reaction rate kinetics
> calculations
> 
> 
> Sent to CCL by: "Ted  Dibble" [tsdibble{:}syr.edu]
> The answers to your questions can be found in most textbooks.  Start
> with a
> physical chemistry textbook for the basics, and look in a graduate
> kinetics
> textbook for fuller explanations.  Look for the Lindeman or Lindeman-
> Hinshelwood mechanism.
> 
>    The three-body reaction is the net reaction including the third
> body, e.g.:
>        ClO + NO2 + M  =  ClONO2 + M
> where M is the third body, and [M] corresponds to the total
> concentration of
> gas phase species.  This is in contrast to the elementary reactions:
>       ClO + NO2  ->  ClONO2*
>       ClONO2*   ->  ClO + NO2
>       ClONO2*  + M   ->  ClONO2  + M
> 
> Please note:  TST applies where there is a Boltzmann distribution of
> energy,
> which corresponds to the high-pressure limit rather than the low-
> pressure
> limit.
> 
>    To calculate rate constants versus pressure, see the UNIMOL package,
> made
> available at http://www.frad.t.u-tokyo.ac.jp/miyoshi/ssumes/index.html
> 
> Good luck!
> 
> Theodore S. Dibble
> Chemistry Department
> SUNY-Environmental Science and Forestry
> 1 Forestry Drive
> Syracuse, NY 13210
> (315) 470-6596
> (315) 470-6856  (fax)
> http://www.esf.edu/chemistry/faculty/dibble.htm
> 
> 
> > "RD Miles rdmsgl!A!gmail.com"  wrote:
> >
> > Sent to CCL by: RD Miles [rdmsgl^gmail.com]
> > --0015173fe52af75fe4049efe5381
> > Content-Type: text/plain; charset=ISO-8859-1
> >
> > I have been working on calculating reaction rate constants at the low
> > pressure limit using TST type methodologies. However, I need to
> understand
> > how to transition into calculations for high pressure systems.
> >
> > Could you recommend any references that deal specifically with the
> pressure
> > dependence of reaction rate constants, and how it is addressed in
> > computational chemistry?
> >
> > Questions I have are:
> >
> >    - Can TST based methods be adapted to high pressure systems?
> >    - What is meant by "3 body reactions" in many kinetics mechanisms?
> >    - What is meant by the pressure dependence "fall-off" in some
> reaction
> >    rate constant descriptions?
> >
> > Any help on this subject would be greatly appreciated.
> >
> > -RD> To recover the email address of the author of the message, please
> change