[molpro-user] Linear dependent basis

[Kirk Peterson]

John,

could you send your basis set block to me?

best wishes,

Kirk


On Jul 12, 2010, at 3:11 AM, John Keith wrote:

> Hi all,
> 
> I'm trying to run single reference ab initio calculations on
> transition metal complexes and build up enough calculations to
> extrapolate to the CBS limit.
> 
> My molecule is the PdCl4 dianion, and I'm using the Stuttgart Pd
> pseudopotential and the (aug)-cc-pvNZ basis sets on all other valence
> electrons. All are taken from the EMSL basis set library. I get SCF
> convergence with cc-pvDZ, aug-cc-pvDZ, cc-pvTZ, and aug-cc-pvTZ basis
> sets, but at cc-pvQZ I run into an error saying:
> 
> ------------------------
> Eigenvalues of metric
> 
>         1 0.212E-08 0.406E-05 0.681E-05 0.681E-05 0.835E-05 0.102E-04
> 0.103E-04 0.106E-04
> 
> ERROR: BASIS LINEARLY DEPENDENT OR WRONG S
> 
> The current threshold for the smallest tolerated eigenvalue of S is   1.0D-08
> ------------------------
> 
> I spent some time searching the user-list and google, and I couldn't
> find a solution I needed.  What I gather is that since my geometries
> are reasonable, the jobs run fine with smaller basis sets, and since I
> only have one eigenvalue below the threshold, this error probably just
> comes from the fact my QZ basis is (not surprisingly) linearly
> dependent and should be scaled down one or a few basis functions.
> 
> Pardon the naive question, but does someone know the "right" way to
> modify this basis set so it is not linearly dependent, but that it is
> also of desired quality for a meaningful CBS extrapolation? Is it as
> straightforward as starting at the QZ basis and removing individual
> diffuse functions until the basis set is not linearly dependent, or is
> there a higher art to it?
> 
> My input file is:
> ***Pd_4Cl
> 
> cartesian
> 
> geomtyp=xyz
> orient,mass
> geometry={
> 5
> Pd_4Cl calc
> Pd   -0.213992    0.027380   -0.117721
> Cl   -1.943705   -1.515957    0.437439
> Cl    1.304488   -1.784426   -0.423439
> Cl    1.515859    1.570547   -0.672946
> Cl   -1.732472    1.839247    0.188003
> }
> set,charge=-2
> 
> <BASIS>
> 
> hf
> 
> In my <BASIS> block, I've been using a script to pasting the explicit
> basis sets from the EMSL website into the input file. I don't want to
> paste all those messy numbers here unless that's actually requested.
> 
> Thanks in advance!
> 
> --john
> 
> #####################################################################
> Ph D. John A. Keith
> Institut für Elektrochemie     Email: john.keith at uni-ulm.de
> Universität Ulm                    Telephone: +49-731-50-26061
> Albert-Einstein-Allee 47       URL: http://www.wag.caltech.edu/home/johnk
> Ulm D-89069                       URL:
> http://www.uni-ulm.de/theo_echem/index.shtml
> #####################################################################
> There is as much difference between us and ourselves as between us and others.
> 
> -Michel de Montaigne, essayist (1533-1592)
> #####################################################################
> _______________________________________________
> Molpro-user mailing list
> Molpro-user at molpro.net
> http://www.molpro.net/mailman/listinfo/molpro-user