[molpro-user] Extrapolation to the complete basis set limit of def2-anzvp basis sets.
Tatiana Korona
tania at tiger.chem.uw.edu.pl
Fri Oct 25 10:46:56 BST 2013
Dear Sasha and Kirk,
Although def2-basis sets were not designed for basis set extrapolation they can
be used for estimating CBS and this is shown e.g. in works of Frank Neese and
collaborators, see
Anoop, A.; Thiel, W.; Neese, F. J. Chem. Theory Comput. 2010, 6, 3137.
Neese, F.; Valeev, E. F. J. Chem. Theory Comput. 2011, 7, 33.
I also used the usual formula E(Basis[X]) = E(CBS) + A/X^3 for X=3 and 4 for
def2-TZVP and def2-QZVP several times and the results seem to be encouraging.
Best wishes,
Tatiana
On Wed, 23 Oct 2013, Peterson, Kirk wrote:
> Dear Alexander (Sasha),
>
> 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.
>
> best,
>
> -Kirk
>
> 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-
>
>
> On Oct 23, 2013, at 5:17 AM, sasha medvedev <vinsanity305 at mail.ru<mailto:vinsanity305 at mail.ru>> wrote:
>
> Dear molpro users.
> We calculate ab initio potentials of alkali metal - inert gase weakly bound molecules.
> 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) .
> 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:
> For Cs:
> def2-asvp
> Library entry Cs ECP ECP46MDF selected for group 1
> Library entry CS S def2-SVP selected for orbital group 1
> Even tempered Cs S diffuse selected for group 1 nprim= 1 centre= 0.005 ratio= 2.271 dratio= 1.000
> Library entry CS P def2-SVP selected for orbital group 1
> Even tempered Cs P diffuse selected for group 1 nprim= 1 centre= 0.003 ratio= 5.198 dratio= 1.000
> Library entry CS D def2-SVP selected for orbital group 1
> Even tempered Cs D diffuse selected for group 1 nprim= 1 centre= 0.008 ratio= 4.004 dratio= 1.000
>
> def2-atzvp
> Library entry Cs ECP ECP46MDF selected for group 1
> Library entry CS S def2-TZVP selected for orbital group 1
> Even tempered Cs S diffuse selected for group 1 nprim= 1 centre= 0.005 ratio= 2.271 dratio= 1.000
> Library entry CS P def2-TZVP selected for orbital group 1
> Even tempered Cs P diffuse selected for group 1 nprim= 1 centre= 0.003 ratio= 5.198 dratio= 1.000
> Library entry CS D def2-TZVP selected for orbital group 1
> Even tempered Cs D diffuse selected for group 1 nprim= 1 centre= 0.004 ratio= 3.904 dratio= 1.000
>
> For Rb:
> def2-asvp
> Library entry Rb ECP ECP28MDF selected for group 2
> Library entry RB S def2-SVP selected for orbital group 2
> Even tempered Rb S diffuse selected for group 2 nprim= 1 centre= 0.006 ratio= 2.320 dratio= 1.000
> Library entry RB P def2-SVP selected for orbital group 2
> Even tempered Rb P diffuse selected for group 2 nprim= 1 centre= 0.003 ratio= 6.503 dratio= 1.000
> Library entry RB D def2-SVP selected for orbital group 2
> Even tempered Rb D diffuse selected for group 2 nprim= 1 centre= 0.003 ratio= 8.238 dratio= 1.000
>
> def2-atzvp
> Library entry Rb ECP ECP28MDF selected for group 1
> Library entry RB S def2-TZVP selected for orbital group 1
> Even tempered Rb S diffuse selected for group 1 nprim= 1 centre= 0.006 ratio= 2.287 dratio= 1.000
> Library entry RB P def2-TZVP selected for orbital group 1
> Even tempered Rb P diffuse selected for group 1 nprim= 1 centre= 0.006 ratio= 2.500 dratio= 1.000
> Library entry RB D def2-TZVP selected for orbital group 1
> Even tempered Rb D diffuse selected for group 1 nprim= 1 centre= 0.003 ratio= 3.569 dratio= 1.000
>
> 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).
> --------------------------------------------------------------------------------------------------------------------------------------
> 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 should be equal to the lmax). When we looked through output file, we noticed, that the same basis set has different lmax for different atoms:
>
> For Cs (def2-aqzvp basis set with ecp46mdf)
>
> Library entry Cs ECP ECP46MDF selected for group 2
> Library entry AR S def2-QZVP selected for orbital group 1
> Even tempered Ar S diffuse selected for group 1 nprim= 1 centre= 0.068 ratio= 2.441 dratio= 1.000
> Library entry AR P def2-QZVP selected for orbital group 1
> Even tempered Ar P diffuse selected for group 1 nprim= 1 centre= 0.044 ratio= 2.497 dratio= 1.000
> Library entry AR D def2-QZVP selected for orbital group 1
> Even tempered Ar D diffuse selected for group 1 nprim= 1 centre= 0.123 ratio= 2.407 dratio= 1.000
> Library entry AR F def2-QZVP selected for orbital group 1
> Even tempered Ar F diffuse selected for group 1 nprim= 1 centre= 0.223 ratio= 2.440 dratio= 1.000
> Library entry AR G def2-QZVP selected for orbital group 1
> Even tempered Ar G diffuse selected for group 1 nprim= 1 centre= 0.403 ratio= 2.500 dratio= 1.000
>
> Library entry CS S def2-QZVP selected for orbital group 2
> Even tempered Cs S diffuse selected for group 2 nprim= 1 centre= 0.008 ratio= 1.465 dratio= 1.000
> Library entry CS P def2-QZVP selected for orbital group 2
> Even tempered Cs P diffuse selected for group 2 nprim= 1 centre= 0.004 ratio= 2.468 dratio= 1.000
> Library entry CS D def2-QZVP selected for orbital group 2
> Even tempered Cs D diffuse selected for group 2 nprim= 1 centre= 0.004 ratio= 2.911 dratio= 1.000
> Library entry CS F def2-QZVP selected for orbital group 2
> Even tempered Cs F diffuse selected for group 2 nprim= 1 centre= 0.235 ratio= 2.500 dratio= 1.000
>
> For Rb (def2-qzvp with ecp28mdf)
>
> Library entry Rb ECP ECP28MDF selected for group 2
> Library entry AR S def2-QZVP selected for orbital group 1
> Even tempered Ar S diffuse selected for group 1 nprim= 1 centre= 0.068 ratio= 2.441 dratio= 1.000
> Library entry AR P def2-QZVP selected for orbital group 1
> Even tempered Ar P diffuse selected for group 1 nprim= 1 centre= 0.044 ratio= 2.497 dratio= 1.000
> Library entry AR D def2-QZVP selected for orbital group 1
> Even tempered Ar D diffuse selected for group 1 nprim= 1 centre= 0.123 ratio= 2.407 dratio= 1.000
> Library entry AR F def2-QZVP selected for orbital group 1
> Even tempered Ar F diffuse selected for group 1 nprim= 1 centre= 0.223 ratio= 2.440 dratio= 1.000
> Library entry AR G def2-QZVP selected for orbital group 1
> Even tempered Ar G diffuse selected for group 1 nprim= 1 centre= 0.403 ratio= 2.500 dratio= 1.000
>
> Library entry RB S def2-QZVP selected for orbital group 2
> Even tempered Rb S diffuse selected for group 2 nprim= 1 centre= 0.006 ratio= 2.064 dratio= 1.000
> Library entry RB P def2-QZVP selected for orbital group 2
> Even tempered Rb P diffuse selected for group 2 nprim= 1 centre= 0.005 ratio= 2.591 dratio= 1.000
> Library entry RB D def2-QZVP selected for orbital group 2
> Even tempered Rb D diffuse selected for group 2 nprim= 1 centre= 0.003 ratio= 2.877 dratio= 1.000
> Library entry RB F def2-QZVP selected for orbital group 2
> Even tempered Rb F diffuse selected for group 2 nprim= 1 centre= 0.341 ratio= 2.500 dratio= 1.000
>
> So, def2-aqzvp basis set can change its cardinal number n, but it is still called aqzvp!
> 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?
>
> So, it is impossible to extrapolate the energy of the system, which contains atoms with different lmax (when we use def2-anzvp
> 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?
>
> 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).
>
> Alexander Medvedev,
> student of the 5th course of
> Lomonosov Moscow State University
> Department of Chemistry
> Chair of Laser Chemistry
>
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>
Dr. Tatiana Korona http://tiger.chem.uw.edu.pl/staff/tania/index.html
Quantum Chemistry Laboratory
University of Warsaw
Pasteura 1, PL-02-093 Warsaw, POLAND
`The man who makes no mistakes does not usually make anything.'
Edward John Phelps (1822-1900)
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