CCL: calcualtion of kinetic isotopic effect values
- From: Sebastian Kozuch <kozuchs[a]yahoo.com>
- Subject: CCL: calcualtion of kinetic isotopic effect values
- Date: Thu, 29 Mar 2012 10:17:09 -0700 (PDT)
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, 3066â3072.
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>, 3066â3072.</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 is
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