<html xmlns:v="urn:schemas-microsoft-com:vml" xmlns:o="urn:schemas-microsoft-com:office:office" xmlns:w="urn:schemas-microsoft-com:office:word" xmlns:m="http://schemas.microsoft.com/office/2004/12/omml" xmlns="http://www.w3.org/TR/REC-html40"> <head> <meta http-equiv="Content-Type" content="text/html; charset=utf-8"> <meta name="Generator" content="Microsoft Word 14 (filtered medium)"> <style></style> </head> <body lang="EN-GB" link="blue" vlink="purple"> <div class="WordSection1"> <p class="MsoNormal"><span style="font-size:11.0pt;font-family:"Calibri","sans-serif";color:#1F497D">Dear Daniel<o:p></o:p></span></p> <p class="MsoNormal"><span style="font-size:11.0pt;font-family:"Calibri","sans-serif";color:#1F497D"><o:p> </o:p></span></p> <p class="MsoNormal"><span style="font-size:11.0pt;font-family:"Calibri","sans-serif";color:#1F497D">Did you try to restart with DIAGONALISATION and ADDED_MOS using a wavefunction restart file from a well-converged OT run?<o:p></o:p></span></p> <p class="MsoNormal"><span style="font-size:11.0pt;font-family:"Calibri","sans-serif";color:#1F497D"><o:p> </o:p></span></p> <p class="MsoNormal"><span style="font-size:11.0pt;font-family:"Calibri","sans-serif";color:#1F497D">Best regards<o:p></o:p></span></p> <p class="MsoNormal"><span style="font-size:11.0pt;font-family:"Calibri","sans-serif";color:#1F497D"><o:p> </o:p></span></p> <p class="MsoNormal"><span style="font-size:11.0pt;font-family:"Calibri","sans-serif";color:#1F497D">Matthias<o:p></o:p></span></p> <p class="MsoNormal"><span style="font-size:11.0pt;font-family:"Calibri","sans-serif";color:#1F497D"><o:p> </o:p></span></p> <p class="MsoNormal"><b><span lang="EN-US" style="font-size:10.0pt;font-family:"Tahoma","sans-serif"">From:</span></b><span lang="EN-US" style="font-size:10.0pt;font-family:"Tahoma","sans-serif""> cp...@googlegroups.com [mailto:cp...@googlegroups.com] <b>On Behalf Of </b>Dan_M<br> <b>Sent:</b> 10 May 2018 13:46<br> <b>To:</b> cp2k<br> <b>Subject:</b> [CP2K:10298] Re: MO coefficients not normalized?<o:p></o:p></span></p> <p class="MsoNormal"><o:p> </o:p></p> <div> <p class="MsoNormal"><br> Thanks a lot Matt for your very fast answer. I was so concerned with technical issues that I forgot about the basics.<br> <br> Actually maybe you or some other expert can help me out with the actual issue I am having. The situation is this:<br> <br> I want to get the MOs (eigenvalues and eigenvectors) for both the occupied and unoccupied states in a somewhat involved system (~100-200 waters plus one proton, i.e. total charge +1, geometry let's say far from any local minima). For this I tried two routes:<br> <br> 1) converge the wfn with OT and request NLUMO to be computed after convergence. With this I find two problems:<br> - The calculation of the LUMOs does not converge (I get "WARNING : did not converge in ot_eigensolver" even if I increase MAX_ITER_LUMO to 1000 which I think should be enough). I note that I could get it converged for EPS_LUMO 1.0E-4 but I tried with a much tighter convergence (2.0E-07 as with the occupied states) since what I get otherwise is the energy of the LUMO below that of the HOMO. I am aware of this happening often when the system is metallic and OT is not well suited but I think it should not happen in a protonated water system (I would expect finding the LUMO as a lone state somewhere in the middle of the band gap, but not this).<br> - Even when it converges (which I managed to do in toy systems but not on my system of interest), this only works for getting the eigenvalues which can be done either requesting the NLUMO in the &PDOS or in the &MO_CUBES sections, but not the eigenvectors even if I try to do the trick of asking for MO_INDEX_RANGE 1 [nhomo+nlumo] in the &MO section.<br> <br> 2) converge the wfn with diagonalization in any flavor (standard, davidson, lanczos or filter_matrix) requesting ADDED_MOS. Here the problem is that the diagonalization is a complete pain and I am struggling a lot to get it converged, which I did not manage yet. I am trying to do the usual tricks (playing with the ALPHA in &MIXING, etc), but still I have not managed to converge it. I tried doing the trick of computing the wfn with OT and then use that wfn as guess in a run with diagonalization with ADDED_MOS, but in that case the coefficients seem to be rescaled or ignored (since there are less MOS in the restart wfn than expected) and I don't get any improvement.<br> <br> Maybe somebody could give me some tips for improving the diagonalization in charged systems (some combination of mixing methods, parameters, etc.) or some workaround to make it work with OT?<br> <br> Thanks again!<br> D.<br> <br> <br> El miércoles, 9 de mayo de 2018, 22:21:37 (UTC+2), Matt W escribió:<o:p></o:p></p> <div> <p class="MsoNormal">Dear Daniel,<o:p></o:p></p> <div> <p class="MsoNormal"><o:p> </o:p></p> </div> <div> <p class="MsoNormal">the Gaussian basis set is not orthonormal, so the overlap matrix is required to provide a metric that converts to an orthonormal basis. Due to symmetry the pz orbital is orthogonal to the others in your example, so in that case every thing is easy.<o:p></o:p></p> </div> <div> <p class="MsoNormal"><o:p> </o:p></p> </div> <div> <p class="MsoNormal">In general, the relation is C^T S C = I, where C is the matrix of MO coefficients, S is the overlap matrix and I is the identity matrix. You can print of the S matrix and check this. It is somewhere in the AO_MATRICES section of DFT % PRINT.<o:p></o:p></p> </div> <div> <p class="MsoNormal"><o:p> </o:p></p> </div> <div> <p class="MsoNormal">See, for instance, Szabo and Ostlund, Modern Quantum Chemistry, Introduction to Advanced Electronic Structure Theory - exercise 3.10 in my version.<o:p></o:p></p> </div> <div> <p class="MsoNormal"><o:p> </o:p></p> </div> <div> <p class="MsoNormal">Matt<br> <br> On Wednesday, May 9, 2018 at 8:20:13 PM UTC+1, Dan_M wrote:<o:p></o:p></p> <div> <p class="MsoNormal" style="margin-bottom:12.0pt">Dear all,<br> <br> After requesting the printing out of the MO coefficients, I have observed that the coefficients do not seem to be normalized. For instance, here are the MOs for 1 water molecule with a SZV basis (after a single point calculation on the "real" geometry, with diagonalization algorithm standard):<br> <br> MO EIGENVALUES, MO OCCUPATION NUMBERS, AND SPHERICAL MO EIGENVECTORS<br> <br> 1 2 3 4<br> -0.952554 -0.496599 -0.304175 -0.250528<br> <br> 2.000000 2.000000 2.000000 2.000000<br> <br> 1 1 O 2s 0.807460 -0.000000 0.542312 0.000000<br> 2 1 O 3py -0.246487 -0.000000 0.810927 0.000000<br> 3 1 O 3pz -0.000000 0.000000 -0.000000 1.000000<br> 4 1 O 3px 0.000000 -0.661844 -0.000000 -0.000000<br> <br> 5 2 H 1s 0.125677 -0.390214 -0.194623 -0.000000<br> <br> 6 3 H 1s 0.125677 0.390214 -0.194623 -0.000000<br> <br> So only the MO 4 is trivially normalized, but the others are not. Am I missing something (some correction factor, etc) or is this just the way it is?<br> <br> Thanks and best<br> Daniel<o:p></o:p></p> </div> </div> </div> </div> <p class="MsoNormal">-- <br> You received this message because you are subscribed to the Google Groups "cp2k" group.<br> To unsubscribe from this group and stop receiving emails from it, send an email to <a href="mailto:cp2k+unsu...@googlegroups.com">cp2k+unsu...@googlegroups.com</a>.<br> To post to this group, send email to <a href="mailto:cp...@googlegroups.com">cp...@googlegroups.com</a>.<br> Visit this group at <a href="https://groups.google.com/group/cp2k">https://groups.google.com/group/cp2k</a>.<br> For more options, visit <a href="https://groups.google.com/d/optout">https://groups.google.com/d/optout</a>.<o:p></o:p></p> </div> </body> </html>