<html><head><meta http-equiv="Content-Type" content="text/html charset=us-ascii"></head><body style="word-wrap: break-word; -webkit-nbsp-mode: space; -webkit-line-break: after-white-space;">Dear Alexander,<div><br></div><div>looks to me like clearly the 2c basis set has some significant linear dependency problems from the p functions. This is shown in the bottom of the integral output:</div><div><br></div><div><div> Eigenvalues of metric</div><div><br></div><div> 1 0.439E-07 0.617E-03 0.729E-02 0.114E-01 0.379E-01 0.508E-01 0.143E+00 0.181E+00</div><div> 2 0.439E-07 0.114E-01 0.508E-01 0.143E+00 0.188E+00 0.389E+00 0.509E+00 0.665E+00</div><div> 3 0.439E-07 0.114E-01 0.508E-01 0.143E+00 0.188E+00 0.389E+00 0.509E+00 0.665E+00</div><div> 4 0.188E+00 0.509E+00 0.665E+00 0.100E+01 0.100E+01 0.124E+01 0.134E+01 0.207E+01</div><div><br></div><div>Those 3 very small eigenvalues are the clue what the problem is. The 1c basis set doesn't have this issue. Notice in the 2c basis set that primitive #3 from the original p set has an exponent of 0.47666322385 (which is actually uncontracted) and the 2nd extra p function that is included in the 2c set is nearly identical, 0.4782. I would just remove that last extra p and then you should be fine.</div><div><br></div><div>best regards,</div><div><br></div><div>-Kirk</div><div><br></div><div><br></div><div><div>On Apr 23, 2014, at 1:02 PM, sasha medvedev <<a href="mailto:vinsanity305@mail.ru">vinsanity305@mail.ru</a>> wrote:</div><br class="Apple-interchange-newline"><blockquote type="cite">
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<div>Hello, molpro users and developers.<br><br>I met a rather strange result: <br>uccsd(t) calculation for a Cs atom did not converge,<br>when I used dhf-qzvp-2c basis set. <br><br>So, the ending of the output file was as following:<br><br> ? Error<br> ? No convergence. This error exit can be avoided using the NOCHECK option<br> ? The problem occurs in ccsd<br><br>Here is the code (I also attached the appropriate input file to this mail):<br>***<br>gthresh,energy=1.d-8,orbital=1.d-8,coeff=1.d-7<br>....<br>symmetry,x,y<br>geometry={Cs}<br>{rhf;occ,3,1,1,0;core,0,0,0,0;wf,9,1,1;}<br>{uccsd(t);core,0,0,0,0;wf,9,1,1;}<br>...<br><br>I should note, that the dhf-qzvp-1c set converges in such calculation (you can run the attached input file - it contains both sets).<br>And, by the way, the difference between -1c and -2c set is only in two
p-functions, which are added to take into account spin-orbit effects.<br>Of course, I see that the result depends on global thresholds [so, calculations with dhf-qzvp-2c set converge for bigger thresholds; <br>for instance with: gthresh,energy=1.d-6,orbital=1.d-5,coeff=1.d-5 ]. <br>But it still seems to be strange, that almost the same basis set doesn't converge in the <br>same routine.<br><br>I use molpro2010, so I take dhf basis sets here: <a href="http://www.cosmologic.de/basis-sets/basissets.php" target="_blank">http://www.cosmologic.de/basis-sets/basissets.php</a><br><br>Alexander Medvedev,<br>student of the 5th course,<br>MSU, Chemistry Department,<br>Chair of laser chemistry<br></div>
<span><Cs_dhf-qzvp-1c_2c.inp></span>_______________________________________________<br>Molpro-user mailing list<br><a href="mailto:Molpro-user@molpro.net">Molpro-user@molpro.net</a><br>http://www.molpro.net/mailman/listinfo/molpro-user</blockquote></div><br></div></body></html>