Well, for a catalytic cycle, to = find the TOF determining intermediate and transition state (TDI and TDTS) y= ou have a couple of ways:

I) The most "analytical" and less intuitiv= e is to calculate them with the degree of TOF control (eqs. 11 and 12 in th= e paper). The states with higher degree are determining.

II) Look fo= r all the combinations of energies of the transition states and intermediat= es according to eq 9:

dE =3D E(TS) - E(I) &nb= sp; &n= bsp; if the intermediate= comes before the TS
=3D E(TS) - E(I) + DGr &nbs= p; if the intermediate comes after the TS (DGr is the reaction energy of the = whole cycle)

the combination that maximizes dE (the energetic span) = are the TDI and TDTS.

III) The visual way is to draw the cycles two = consecutive times and for each intermediate look for the highest TS in the = forward direction. The biggest difference will give you the energetic span = and the determining states. It is a bit hard to draw it here, but you'll fi= nd the schematics in figure 11 of the account, or in ChemPhysChem, 2011, 12= , 1413 and in J Phys Chem A 2008, 112, 6032.

IV) Put all the energie= s data in the AUTOF program and let it calculate the determining states for= you (it uses the degree of TOF control for that).

Applying any = of the methods you will receive that in the first example (figure 1), for t= he 6 links catalyst the TDTS is the oxidative addition, which is indeed the= highest point in the graph (the reductive elimination is almost as important as the ox. add. though). For the 3 links catalyst the reductive = elimination is more important. For both reactions the TDI is the lowest poi= nt in the cycle. I can say that the determining states are not necessarily the highest and lowest st= ates, but depending on the system they can certainly be.

Best= ,

Sebastian Kozuch

From: JL je= ffrey.lebowski:+:gmx.de <owner-chemistry|*|ccl.net>
To: "Kozuch, Sebastian " <koz= uchs|*|yahoo.com>
Sent: Wednesday, June 8, 2011 1:23 PM
Subject: CCL: AW: activation barrier

=0ASent to CCL by: "JL" [jeffrey.lebowski++gmx.de]
Dear Mr. Kozuch
I read your paper (Acc. Chem. Res. 2011 , 44 , 101-110) and I just d= on't
get how to determine the TDI and TDTS. Obviously they are not just = the
highest and lowest point in the mechanism energy scheme. How have th= ey been
determined for the first example (figure 1, PhCl to PhSH via Pd = catalyst)?

Can you say anything about that?

Many thanks in ad= vance!

Cheers!

-----Urspr=FCngliche Nachricht-----
Betreff: CCL: activation barrier

No. 30 Kcal/mol is a barrier t= hat can only be surmounted at high
temperature. Check it looking at Eyri= ng's transition state theory.
By the way, two important points to take i= nto account. First, you must use
Gibbs energies, and not only internal e= nergies. Second, in a catalytic
reaction the global rate is not dependen= t on only one barrier, but on the
energetic span. Take a look atAcc. Chem. Res. 2011 , 44 ,

101-110 = ; &nbs= p; . It may be useful
for you to check o= ur AUTOF program, J. Comput. Chem. 2011 , 32 ,

978-985 &n= bsp; &= nbsp; (sorry for the
self-p= ublicity).

Best,

xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx= xxx
..........Sebastian Kozuch...........
xxxxxxxxxxxxxxxxxxxxxxxxxxx= xxxxxxxxxx
....Weizmann Institute of Science....
...........Rehovot, = Israel...........
.. sebastian.kozuch[A]weizmann.ac.il ..
http://yfaat.ch.huji.ac.il/koz= uch.htm
xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx

_______________= _________________
> From: Abhishek Dutta Chowdhury abhishekdc[]iitb.ac.in
<owner-c= hemistry[A]ccl.net>
= To: "Kozuch, Sebastian " <kozuchs[A]yahoo.com>
Sent: Wednesday, June 8, 2011 5:56 AM
Su= bject: CCL: activation barrier

Sent to CCL by: "Abhishek D= utta Chowdhury" [abhishekdc(0)iitb.ac.in]
Hi ALL:
What is the = maximum energy limit of activation barrier in any catalytic
reaction at = RT (at B3LYP level of theory)? Is it can go beyond 30 KCal/mol??

Man= y thanks in advance.

best wishes,
Abhishekthe strange characters = on the top line to the [A] sign. You can also

= E-mail to administrators: CHEMISTRY-REQUEST[A]ccl.net or use
= ; --0-477340988-130751= 3858=3D065
Content-Type: text/html; charset=3Do-8859-1
Content-Transfer-Encoding: quoted-printable

&= lt;html><body><div style=3D"color:#000; background-color:#fff;<= br>font-family:arial, helvetica, sans-serif;font-size:10pt"><div>&= lt;span>No. 30
Kcal/mol is a barrier that can only be surmounted at h= igh temperature. Check
it looking at Eyring's transition state theory.&l= t;/span></div><div>By
the way, two important = points to take into account. First, you must use
Gibbs energies, and not= only internal energies. Second, in a catalytic
reaction the global rate= is not dependent on only one barrier, but on the
energetic span. Take a= look at &l= t;i>Acc. Chem. Res.

 &= nbsp; &nb= sp;
 &n= bsp;
2011 = = ;
 = , =
 &n= bsp; &nbs= p;
44 &nbs= p; &nb= sp;
 = , = ;
101-110 = ;
 &= nbsp; . It may be useful for you to check our AUTOF
program, </font&g= t;

 = ; &= nbsp;
J. Comput. Chem. = ; &nbs= p;
 = &= nbsp;
 &n= bsp; = ;
2011 &n= bsp; &= nbsp;
 , =
 &= nbsp; &nbs= p;
32 &nb= sp; &n= bsp;
 &nbs= p; , &nbs= p;
978-985 = ; &nbs= p;
 (sorr= y for the
self-publicity).</div><div> </= div><div>Best,&= lt;br></div><div> </div><div>xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx ..........= Sebastian Kozuch........... xxxxxxxxxxxxxxxxxxxxxxxxxxxxxx= xxxxxxx ....Weizmann
Institute of Science....= <sp= an style=3D"font-family:courier, monaco, monospace,
sans-serif;">....= .......Rehovot, Israel........... ..
sebas= tian.kozuch[A]weizmann.ac.il .. <a rel=3D"nofollow" target= =3D"_blank"
href=3D"http://yfaat.ch.huji.ac.il/kozuch.htm">http://yfaat.c= h.huji.ac.il/kozuch.htm</a> xxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx</= span> </div><div
style=3D"font-family: arial, helve= tica, sans-serif; font-size: 10pt;"><div
style=3D"font-family: tim= es new roman, new york, times, serif; font-size:
12pt;"><hr size=3D"1">From: Abhishek Dutta Chowdhur= y
abhishekdc[]iitb.ac.in <owner-chemistry[A]ccl.net><b= r>To:&= lt;/b> "Kozuch, Sebastian "
<kozuchs[A]yahoo.com><br= >Sent:= Wednesday, June 8, 2011 5:56 AM Subject: CCL: activation
barrier 
 Sent t= o CCL by: "Abhishek  Dutta Chowdhury" [abhishekdc(0)<a
targe= t=3D"_blank" href=3D"http://iitb.ac.in">iitb.ac.in</a>] H= i
ALL:   What is the maximum energy limit of activatio= n barrier in any
catalytic reaction at RT (at B3LYP level of theory)? Is= it can go beyond 30
KCal/mol?? Many thanks in advanc= e. best
wishes, Abhishek = <br<br the strange characters on the top
line t= o the [A] sign. You can also<br E-mail to subscribers= : <a
ymailto=3D"mailto:CHEMISTRY[A]ccl.net"
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to administrators: &l= t;a ymailto=3D"mailto:CHEMISTRY-REQUEST[A]ccl.net"
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