<HTML><BODY>Hello, professor Kirk Peterson.<br>1) It's great that you have clarified the situation with extrapolation properties of def2- basis sets.<br>Unfortunately, they were not designed for it.<br>2) And your remark about 3-point extrapolation, involving DZ basis set, is important. <br>3) The last: <br><br>>also, you might want to take a look at the top of the file def2-nzvpp-orb.libmol in your molpro lib directory for some notes about def2- vs. dhf-<br><br>I have checked file def2-nzvpp-orb.libmol:<br><br>lib/def2-nzvpp-orb.libmol $Revision: 2010.1 $ <br>*<br>* Basis sets taken from Turbomole basis set library at<br>* <a href="http://bases.turbo-forum.com/TURBOMOLE_BASISSET_LIBRARY/tbl.html" target="_blank">http://bases.turbo-forum.com/TURBOMOLE_BASISSET_LIBRARY/tbl.html</a><br>* on 2009-11-18.<br>*<br>* Notes:<br>* - In Turbomole, some of the def2- basis sets are associated with slightly<br>* modified versions of Stuttgart-Bonn-Koeln pseudopotentials to account for<br>* non-existing support of higher ECP projectors in Turbomole. In here,<br>* these sets are associated with the original versions of these<br>* ECPs, not the modified def2- ones. This is not likely to cause<br>* noticable changes in energy differences.<br>*<br>* - As with the def2-ECPs, elements 37-48 and 55-80 are associated with<br>* ECPxxMWB ECPs (xx=28 for Rb-Cd, xx=46 for Cs-La, xx=60 for Hf-Hg) while<br>* elements 49-54 and 81-86 are associated with ECPxxMDF ECPs.<br>* The MDF basis sets are newer and supposedly more accurate. Note that<br>* the newer MDF sets in the respective sizes also exist for elements<br>* 37-48 and 55-80, but for consistency with Turbomole, the MWB versions<br>* were chosen also here.<br>*<br>* - Gerald Knizia, 2009-11-20<br>--------------------------------------------------------<br>I can't get your idea about comparison of def2- and dhf- basis set (which should be presented in this file, as far as I understand).<br>May be I have an old version of def2-nzvpp-orb.libmol file?<br>May be you mean those basis sets, which go with MDF ECPs? (def2-nzvp/pp-2c)<br><br> Sasha Medvedev.<br><br>Wednesday, 23 october 2013, 15:25 UTC from "Peterson, Kirk" <kipeters@wsu.edu>:<br>
<blockquote style="border-left:1px solid #0857A6;margin:10px;padding:0 0 0 10px;" class="mailru-blockquote">
<div id="">
<div class="js-helper js-readmsg-msg">
<div id="style_13825419450000000645" class="mr_read__body">
<div id="style_13825419450000000645_BODY">
Dear Alexander (Sasha),
<div><br>
</div>
<div>the def2- basis sets to my knowledge were never designed explicitly for basis set extrapolation. They do provide a series of basis sets that range from small to large, but I am not aware of a study that uses them in CBS extrapolations. You might though
want to consider the TZVPP and QZVPP sets since these have f and g functions, respectively, compared to TZVP and QZVP. In any event if you are using lmax-style extrapolations, you only need 2 basis sets to do this. Typically 3-point extrapolations that include
a DZ-quality set is not recommended except for specialized extrapolation formulas.</div>
<div><br>
</div>
<div>best,</div>
<div><br>
</div>
<div>-Kirk</div>
<div><br>
</div>
<div>PS - also, you might want to take a look at the top of the file def2-nzvpp-orb.libmol in your molpro lib directory for some notes about def2- vs. dhf-</div>
<div><br>
</div>
<div><br>
<div>
<div>On Oct 23, 2013, at 5:17 AM, sasha medvedev <<a target="_blank">vinsanity305@mail.ru</a>> wrote:</div>
<br class="Apple-interchange-newline">
<blockquote type="cite">
<div>Dear molpro users.<br>
We calculate ab initio potentials of alkali metal - inert gase weakly bound molecules.<br>
Our research group uses def2-asvp,atzvp,aqzvp basis sets for extrapolation to a complete basis set limit (2 and 3 point formulae from molpro manual-Lx,LHx,Ex2) .<br>
But we stress, that these basis sets are not suitable for a 3-point extrapolation at all, because the lmax is the same for asvp and atzvp basis sets for Rb and Cs atoms:<br>
<span style="text-decoration: underline;">For Cs</span>:<br>
def2-asvp<br>
Library entry Cs ECP ECP46MDF selected for group 1<br>
Library entry CS S def2-SVP selected for orbital group 1<br>
Even tempered Cs S diffuse selected for group 1 nprim= 1 centre= 0.005 ratio= 2.271 dratio= 1.000<br>
Library entry CS P def2-SVP selected for orbital group 1<br>
Even tempered Cs P diffuse selected for group 1 nprim= 1 centre= 0.003 ratio= 5.198 dratio= 1.000<br>
<span style="text-decoration: underline;">Library entry CS D def2-SVP </span> selected for orbital group 1<br>
Even tempered Cs D diffuse selected for group 1 nprim= 1 centre= 0.008 ratio= 4.004 dratio= 1.000<br>
<br>
def2-atzvp<br>
Library entry Cs ECP ECP46MDF selected for group 1<br>
Library entry CS S def2-TZVP selected for orbital group 1<br>
Even tempered Cs S diffuse selected for group 1 nprim= 1 centre= 0.005 ratio= 2.271 dratio= 1.000<br>
Library entry CS P def2-TZVP selected for orbital group 1<br>
Even tempered Cs P diffuse selected for group 1 nprim= 1 centre= 0.003 ratio= 5.198 dratio= 1.000<br>
<span style="text-decoration: underline;">Library entry CS D def2-TZVP</span> selected for orbital group 1<br>
Even tempered Cs D diffuse selected for group 1 nprim= 1 centre= 0.004 ratio= 3.904 dratio= 1.000<br>
<br>
<span style="text-decoration: underline;">For Rb:</span><br>
def2-asvp<br>
Library entry Rb ECP ECP28MDF selected for group 2<br>
Library entry RB S def2-SVP selected for orbital group 2<br>
Even tempered Rb S diffuse selected for group 2 nprim= 1 centre= 0.006 ratio= 2.320 dratio= 1.000<br>
Library entry RB P def2-SVP selected for orbital group 2<br>
Even tempered Rb P diffuse selected for group 2 nprim= 1 centre= 0.003 ratio= 6.503 dratio= 1.000<br>
<span style="text-decoration: underline;">Library entry RB D def2-SVP</span> selected for orbital group 2<br>
Even tempered Rb D diffuse selected for group 2 nprim= 1 centre= 0.003 ratio= 8.238 dratio= 1.000<br>
<br>
def2-atzvp<br>
Library entry Rb ECP ECP28MDF selected for group 1<br>
Library entry RB S def2-TZVP selected for orbital group 1<br>
Even tempered Rb S diffuse selected for group 1 nprim= 1 centre= 0.006 ratio= 2.287 dratio= 1.000<br>
Library entry RB P def2-TZVP selected for orbital group 1<br>
Even tempered Rb P diffuse selected for group 1 nprim= 1 centre= 0.006 ratio= 2.500 dratio= 1.000<br>
<span style="text-decoration: underline;">Library entry RB D def2-TZVP </span> selected for orbital group 1<br>
Even tempered Rb D diffuse selected for group 1 nprim= 1 centre= 0.003 ratio= 3.569 dratio= 1.000<br>
<br>
So, a 3-point extrapolation is forbidden here, because we need at least 3 basis sets with different lmax (unfortunately, we have only two: atzvp,aqzvp).<br>
--------------------------------------------------------------------------------------------------------------------------------------<br>
Besides that, extrapolation formulae depend on the cardinal number n (which is the part of the basis set name - i.e. 2 for asvp, 3 for atzvp, 4 for aqzvp, and
<span style="text-decoration: underline;">should be equal to the lmax</span>). When we looked through output file, we noticed, that the same basis set has different lmax for different atoms:<br>
<br>
For Cs (def2-aqzvp basis set with ecp46mdf)<br>
<br>
Library entry Cs ECP ECP46MDF selected for group 2<br>
Library entry AR S def2-QZVP selected for orbital group 1<br>
Even tempered Ar S diffuse selected for group 1 nprim= 1 centre= 0.068 ratio= 2.441 dratio= 1.000<br>
Library entry AR P def2-QZVP selected for orbital group 1<br>
Even tempered Ar P diffuse selected for group 1 nprim= 1 centre= 0.044 ratio= 2.497 dratio= 1.000<br>
Library entry AR D def2-QZVP selected for orbital group 1<br>
Even tempered Ar D diffuse selected for group 1 nprim= 1 centre= 0.123 ratio= 2.407 dratio= 1.000<br>
Library entry AR F def2-QZVP selected for orbital group 1<br>
Even tempered Ar F diffuse selected for group 1 nprim= 1 centre= 0.223 ratio= 2.440 dratio= 1.000<br>
<span style="text-decoration: underline;">Library entry AR G def2-QZVP </span> selected for orbital group 1<br>
Even tempered Ar G diffuse selected for group 1 nprim= 1 centre= 0.403 ratio= 2.500 dratio= 1.000<br>
<br>
Library entry CS S def2-QZVP selected for orbital group 2<br>
Even tempered Cs S diffuse selected for group 2 nprim= 1 centre= 0.008 ratio= 1.465 dratio= 1.000<br>
Library entry CS P def2-QZVP selected for orbital group 2<br>
Even tempered Cs P diffuse selected for group 2 nprim= 1 centre= 0.004 ratio= 2.468 dratio= 1.000<br>
Library entry CS D def2-QZVP selected for orbital group 2<br>
Even tempered Cs D diffuse selected for group 2 nprim= 1 centre= 0.004 ratio= 2.911 dratio= 1.000<br>
<span style="text-decoration: underline;">Library entry CS F def2-QZVP</span> selected for orbital group 2<br>
Even tempered Cs F diffuse selected for group 2 nprim= 1 centre= 0.235 ratio= 2.500 dratio= 1.000<br>
<br>
For Rb (def2-qzvp with ecp28mdf)<br>
<br>
Library entry Rb ECP ECP28MDF selected for group 2<br>
Library entry AR S def2-QZVP selected for orbital group 1<br>
Even tempered Ar S diffuse selected for group 1 nprim= 1 centre= 0.068 ratio= 2.441 dratio= 1.000<br>
Library entry AR P def2-QZVP selected for orbital group 1<br>
Even tempered Ar P diffuse selected for group 1 nprim= 1 centre= 0.044 ratio= 2.497 dratio= 1.000<br>
Library entry AR D def2-QZVP selected for orbital group 1<br>
Even tempered Ar D diffuse selected for group 1 nprim= 1 centre= 0.123 ratio= 2.407 dratio= 1.000<br>
Library entry AR F def2-QZVP selected for orbital group 1<br>
Even tempered Ar F diffuse selected for group 1 nprim= 1 centre= 0.223 ratio= 2.440 dratio= 1.000<br>
<span style="text-decoration: underline;">Library entry AR G def2-QZVP </span> selected for orbital group 1<br>
Even tempered Ar G diffuse selected for group 1 nprim= 1 centre= 0.403 ratio= 2.500 dratio= 1.000<br>
<br>
Library entry RB S def2-QZVP selected for orbital group 2<br>
Even tempered Rb S diffuse selected for group 2 nprim= 1 centre= 0.006 ratio= 2.064 dratio= 1.000<br>
Library entry RB P def2-QZVP selected for orbital group 2<br>
Even tempered Rb P diffuse selected for group 2 nprim= 1 centre= 0.005 ratio= 2.591 dratio= 1.000<br>
Library entry RB D def2-QZVP selected for orbital group 2<br>
Even tempered Rb D diffuse selected for group 2 nprim= 1 centre= 0.003 ratio= 2.877 dratio= 1.000<br>
<span style="text-decoration: underline;">Library entry RB F def2-QZVP</span> selected for orbital group 2<br>
Even tempered Rb F diffuse selected for group 2 nprim= 1 centre= 0.341 ratio= 2.500 dratio= 1.000<br>
<br>
So, def2-aqzvp basis set can change its cardinal number n, but it is still called aqzvp!<br>
Does it mean, that we should use different n (i.e. cardinal numbers or lmax of a particular basis set) in the extrapolation formulae for the same basis set, if lmax changes?
<br>
<br>
So, it is impossible to extrapolate the energy of the system, which contains atoms with different lmax (when we use def2-anzvp<br>
basis sets), because in such a case n is not determined (something like (n1+n2)/2 - which is not even an integer). Am I right?<br>
<br>
I am also interested in scientific papers, in which extrapolation to the complete basis set limit of def2-asvp/atzvp/aqzvp basis sets is carried out (if extrapolation is allowed for def2-anzvp basis sets).<br>
<br>
Alexander Medvedev, <br>
student of the 5th course of
<div style="text-align: left;">Lomonosov Moscow State University<br>
Department of Chemistry</div>
<div style="text-align: left;">Chair of Laser Chemistry</div>
<br>
</div>
_______________________________________________<br>
Molpro-user mailing list<br>
<a target="_blank">Molpro-user@molpro.net</a><br>
<a href="http://www.molpro.net/mailman/listinfo/molpro-user" target="_blank">http://www.molpro.net/mailman/listinfo/molpro-user</a><br data-mce-bogus="1"></blockquote>
</div>
<br>
</div>
</div>
</div>
</div>
</div>
</blockquote>
<br>
<br>-- <br>s m<br></BODY></HTML>