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Dear Sasha,
<div><br>
</div>
<div>yes, there was an update to this file by Gerald Knizia in August of 2012. Presumably this is included in the latest production version of Molpro. In this new file most of the previous def2- sets that used the older MWB ECPs have been modified to use
the new MDF ones. These are called dhf- .</div>
<div><br>
</div>
<div>best regards,</div>
<div><br>
</div>
<div>-Kirk</div>
<div><br>
<div>
<div>On Oct 24, 2013, at 1:24 PM, sasha medvedev <<a href="mailto:vinsanity305@mail.ru">vinsanity305@mail.ru</a>> wrote:</div>
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<div>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" <<a href="mailto:kipeters@wsu.edu">kipeters@wsu.edu</a>>:<br>
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<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>
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<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>
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-- <br>
s m<br>
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