CCL: calcualtion of kinetic isotopic effect values
- From: Kenneth Ruud <kenneth.ruud]^[uit.no>
- Subject: CCL: calcualtion of kinetic isotopic effect values
- Date: Thu, 29 Mar 2012 22:48:41 +0200
Sent to CCL by: Kenneth Ruud [kenneth.ruud^^^uit.no]
Hi!
Any program that can calculate vibrationally averaged molecular
properties ought to be able to calculate vibrationally averaged
geometries, thus the difference in geometry for X-D and X-H. Thus, I
would expect CFOUR to be able to do this, as well as Dalton. In
Dalton, this would correspond to what had been denoted the
"effective"
geometry, see e.g. J.Chem.Phys. 112, 2655 (2000).
Best regards,
Kenneth
Kenneth Ruud
Director, CTCC
President, Norwegian Chemical Society
Telephone: +47 77623101
http://www.ctcc.no/people/ruud
On Mar 29, 2012, at 7:17 PM, Sebastian Kozuch kozuchs,,yahoo.com wrote:
Although the X-D and X-H bond distances are very
slightly different,
I don't know any program that can calculate that difference. The
optimizations are done in the Born-Oppenheimer approximation and the
mass of the nuclei are not taken into account, only their charge. As
far as I know (and as far as all QM software know) deuterium and
protium have the same charge, so no reoptimization is necessary.
Anyway, the error of the theoretical method is way bigger than the
difference in the real bond lengths.
Maybe this is a good opportunity to recommend an essay by Simmons
and Hartwig that just appeared in ACIE regarding the analysis of the
KIE for inter and intramolecular competition, an issue that has been
overlooked an has been the root of more than one error:
Angewandte Chemie International Edition 2012, 51, 3066–3072.
Best,
Sebastian.
________________________________
From: Jaccob Madhavan chemjaccob(~)yahoo.co.in <owner-chemistry~!
~ccl.net>
To: "Kozuch, Sebastian " <kozuchs~!~yahoo.com>
Sent: Thursday, March 29, 2012 5:26 PM
Subject: CCL: calcualtion of kinetic isotopic effect values
Sent to CCL by: "Jaccob Madhavan" [chemjaccob _ yahoo.co.in]
Dear Friends,
Greetings! For the calculation of kinetic isotopic effect(KIE)
values, optimization with deutrium is needed or only frequency
calcualtion is enough. Any help in this regard will be highily
appreciated.
with best regards
Jaccob
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<html><body><div style="color:#000;
background-color:#fff; font-
family:arial, helvetica, sans-serif;font-size:
10pt"><div><span>Although the
</span><span>X-D and X-H </
span><span>bond distances are very slightly different, I don't
know
any program that can calculate that difference. The optimizations
are done in the Born-Oppenheimer approximation and the mass of the
nuclei are not taken into account, only their charge. As far as I
know (and as far as all QM software know) deuterium and protium have
the same charge, so no reoptimization is necessary. Anyway, the
error of the theoretical method is way bigger than the difference in
the real bond
lengths.</span></div><div><span><br></span></
div><div><span>Maybe this is a good opportunity to
recommend an
essay by Simmons and Hartwig that just appeared in ACIE regarding
the analysis of the KIE for inter and intramolecular competition, an
issue that has been overlooked an has been the root of more than one
error:</span><br><span></span>
<i>Angewandte Chemie International
Edition</i> <b>2012</b>, <i>51</i>,
3066–3072.</div><div class="csl-
bib-body" style="line-height: 1.35; "><div
class="csl-entry"
style="clear: left; ">
</div>
<span class="Z3988"
title="url_ver=Z39.88-2004&ctx_ver=Z39.88-2004&rfr_id=info
%3Asid%2Fzotero.org%3A2&rft_id=info%3Adoi%2F10.1002%2Fanie.
201107334&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx
%3Ajournal&rft.genre=article&rft.atitle=On%20the
%20Interpretation%20of%20Deuterium%20Kinetic%20Isotope%20Effects%20in
%20C%EF%A3%BFH%20Bond%20Functionalizations%20by%20Transition
%E2%80%90Metal%20Complexes&rft.jtitle=Angewandte%20Chemie
%20International
%20Edition&rft.volume=51&rft.issue=13&rft.aufirst=Eric
%20M&rft.aulast=Simmons&rft.au=Eric%20M
%20Simmons&rft.au=John%20F
%20Hartwig
&
;rft
.date
=
2012
-03
-26
&
;rft
.pages
=
3066
-3072&rft.spage=3066&rft.epage=3072&rft.issn=1521-3773">
</span></div><div><span><br></span></
div>Best,<br>Sebastian.<br><br><div
style="font-family: arial,
helvetica, sans-serif; font-size: 10pt;"> <div
style="font-family:
times new roman, new york, times, serif; font-size: 12pt;">
<div
dir="ltr"> <font face="Arial"
size="2"> <hr size="1"> <b><span
style="font-weight:bold;">From:</span></b>
Jaccob Madhavan
chemjaccob(~)yahoo.co.in
<owner-chemistry~!~ccl.net><br>
<b><span style="font-weight:
bold;">To:</span></b> "Kozuch,
Sebastian " <kozuchs~!~yahoo.com> <br>
<b><span style="font-
weight: bold;">Sent:</span></b> Thursday, March 29,
2012 5:26 PM<br>
<b><span style="font-weight:
bold;">Subject:</span></b> CCL:
calcualtion of kinetic isotopic effect values<br> </font>
</div> <br>
<br>Sent to CCL by: "Jaccob Madhavan"
[chemjaccob _
yahoo.co.in]<br>Dear Friends,<br><br>Greetings! For
the calculation
of kinetic isotopic effect(KIE) values, optimization with deutrium
is needed or only frequency calcualtion is enough. Any help in this
regard will be highily appreciated.<br><br>with best
regards<br>Jaccob<br><br><br><br>-= This
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