<div dir="ltr"><div>Good morning Matthias:</div><div>here, is the result of BSSE application for the case when CP2K suggests a relatively optimal adsorption <br></div><div>of a heterocycle molecule at interface.</div><div><br></div><div></div><div>After including BSSE, it is not too clear how to operate with the computed numbers:</div><div> -BSSE RESULTS -</div>-CP-corrected Total energy: -455.120393 -<br>-1-body contribution: -44.966343 -<br>-1-body contribution: -410.139056 -<br>-2-body contribution: -0.014995 -<br><div>-BSSE-free interaction energy: -0.014995</div><div><br></div><div> <div>because if the BSSE free interaction is -0.014995 Hartree = -39.3693725 kJ/mol.</div><div><br></div><div>This is a huge number, <br></div><div>which is significantly larger that any typical binding <br></div><div>for single cycle aromatic molecules at carbonaceous materials.</div><div><br></div><div> <div>Curiously, <br></div><div>the energies of binding by CP2K without BSSE agree with experimental results relatively well.</div> </div><div><br></div><div>Would the result (after BSSE inclusion) suggest that CP2K theory <br></div><div>is not yet fit to address the physics: <br></div><div>that a reasonable agreement without BSSE should be considered as a blind coincidence, </div><div>and that CP2K would need further improvements?</div><div><br></div><div>Thank you for any comment.</div><div><br></div><div>In any way,</div><div>schönes wochenende.</div><div>:-)</div><div></div><div>With best,</div><div></div><div>Victor<br></div></div><div><br></div></div><br><div class="gmail_quote"><div dir="ltr" class="gmail_attr">On Wed, Oct 19, 2022 at 3:27 PM Krack Matthias (PSI) <<a href="mailto:matthias.krack@psi.ch">matthias.krack@psi.ch</a>> wrote:<br></div><blockquote class="gmail_quote" style="margin:0px 0px 0px 0.8ex;border-left:1px solid rgb(204,204,204);padding-left:1ex"><div class="msg-3681270622169193517"> <div style="overflow-wrap: break-word;" lang="en-CH"> <div class="m_-3681270622169193517WordSection1"> <p class="MsoNormal"><span style="font-size:11pt" lang="DE-CH">Hi Victor<u></u><u></u></span></p> <p class="MsoNormal"><span style="font-size:11pt" lang="DE-CH"><u></u> <u></u></span></p> <p class="MsoNormal"><span style="font-size:11pt" lang="EN-US">As you wrote already, you need to add for each atomic kind the corresponding &KIND section for the GHOST kind like<u></u><u></u></span></p> <p class="MsoNormal"><span style="font-family:Consolas" lang="EN-US"><u></u> <u></u></span></p> <p class="MsoNormal"><span style="font-family:Consolas" lang="EN-US">&KIND C_ghost<u></u><u></u></span></p> <p class="MsoNormal"><span style="font-family:Consolas" lang="EN-US">BASIS_SET DZVP-MOLOPT-GTH<u></u><u></u></span></p> <p class="MsoNormal"><span style="font-family:Consolas" lang="EN-US">GHOST<u></u><u></u></span></p> <p class="MsoNormal"><span style="font-family:Consolas" lang="EN-US">&END KIND<u></u><u></u></span></p> <p class="MsoNormal"><span style="font-size:11pt" lang="EN-US"><u></u> <u></u></span></p> <p class="MsoNormal"><span style="font-size:11pt" lang="EN-US">to get reasonable results.<u></u><u></u></span></p> <p class="MsoNormal"><span style="font-size:11pt" lang="EN-US">Usually, one is interested in the last number, the “BSSE-free interaction energy” which is here the difference of the total energies from run (5) and runs (3) and (4), i.e. (5) – [(3) + (4)]. A positive value implies a repulsive interaction (no binding) after removing the BSSE via the counterpoise (CP) correction.<u></u><u></u></span></p> <p class="MsoNormal"><span style="font-size:11pt" lang="EN-US"><u></u> <u></u></span></p> <p class="MsoNormal"><span style="font-size:11pt" lang="EN-US">HTH<u></u><u></u></span></p> <p class="MsoNormal"><span style="font-size:11pt" lang="EN-US"><u></u> <u></u></span></p> <p class="MsoNormal"><span style="font-size:11pt" lang="EN-US">Matthias<u></u><u></u></span></p> <p class="MsoNormal"><span style="font-size:11pt" lang="EN-US"><u></u> <u></u></span></p> <div style="border-color:rgb(181,196,223) currentcolor currentcolor;border-style:solid none none;border-width:1pt medium medium;padding:3pt 0cm 0cm"> <p class="MsoNormal" style="margin-right:0cm;margin-bottom:12pt;margin-left:36pt"> <b><span style="font-size:12pt;color:black">From: </span></b><span style="font-size:12pt;color:black"><a href="mailto:cp2k@googlegroups.com" target="_blank">cp2k@googlegroups.com</a> <<a href="mailto:cp2k@googlegroups.com" target="_blank">cp2k@googlegroups.com</a>> on behalf of Victor Volkov <<a href="mailto:volkovskr@gmail.com" target="_blank">volkovskr@gmail.com</a>><br> <b>Date: </b>Wednesday, 19 October 2022 at 13:00<br> <b>To: </b><a href="mailto:cp2k@googlegroups.com" target="_blank">cp2k@googlegroups.com</a> <<a href="mailto:cp2k@googlegroups.com" target="_blank">cp2k@googlegroups.com</a>><br> <b>Subject: </b>Re: [CP2K:17902] understanding BSSE print out<u></u><u></u></span></p> </div> <div> <div> <p class="MsoNormal" style="margin-left:36pt"><span style="font-size:11pt">Dear Matthias:<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:36pt"><span style="font-size:11pt">thank you for the kind reply.<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:36pt"><span style="font-size:11pt">I did not wish to be "too specific" about the system in public because the results are under <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:36pt"><span style="font-size:11pt">a peer review.<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:36pt"><span style="font-size:11pt">Here I attach one of the exemplary cases: pyridazine at graphene. <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:36pt"><span style="font-size:11pt">Thank you.<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:36pt"><span style="font-size:11pt">With best regards,<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:36pt"><span style="font-size:11pt">Victor<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:36pt"><span style="font-size:11pt"><u></u> <u></u></span></p> </div> </div> <p class="MsoNormal" style="margin-left:36pt"><span style="font-size:11pt"><u></u> <u></u></span></p> <div> <div> <p class="MsoNormal" style="margin-left:36pt"><span style="font-size:11pt">On Wed, Oct 19, 2022 at 12:12 PM Krack Matthias (PSI) <<a href="mailto:matthias.krack@psi.ch" target="_blank">matthias.krack@psi.ch</a>> wrote:<u></u><u></u></span></p> </div> <blockquote style="border-color:currentcolor currentcolor currentcolor rgb(204,204,204);border-style:none none none solid;border-width:medium medium medium 1pt;padding:0cm 0cm 0cm 6pt;margin-left:4.8pt;margin-right:0cm"> <div> <div> <div> <p class="MsoNormal" style="margin-left:36pt"> <span style="font-size:11pt" lang="DE-CH">Hi Victor</span><span style="font-size:11pt"><u></u><u></u></span></p> <p class="MsoNormal" style="margin-left:36pt"> <span style="font-size:11pt" lang="DE-CH"> </span><span style="font-size:11pt"><u></u><u></u></span></p> <p class="MsoNormal" style="margin-left:36pt"> <span style="font-size:11pt" lang="EN-US">Without the full input, it is difficult to make any suggestion. Do you have a &BSSE section defining the FRAGMENTS?</span><span style="font-size:11pt"><u></u><u></u></span></p> <p class="MsoNormal" style="margin-left:36pt"> <span style="font-size:11pt" lang="EN-US"> </span><span style="font-size:11pt"><u></u><u></u></span></p> <p class="MsoNormal" style="margin-left:36pt"> <span style="font-size:11pt" lang="EN-US">Best</span><span style="font-size:11pt"><u></u><u></u></span></p> <p class="MsoNormal" style="margin-left:36pt"> <span style="font-size:11pt" lang="EN-US"> </span><span style="font-size:11pt"><u></u><u></u></span></p> <p class="MsoNormal" style="margin-left:36pt"> <span style="font-size:11pt" lang="EN-US">Matthias</span><span style="font-size:11pt"><u></u><u></u></span></p> <p class="MsoNormal" style="margin-left:36pt"> <span style="font-size:11pt" lang="EN-US"> </span><span style="font-size:11pt"><u></u><u></u></span></p> <div style="border-style:solid none none;border-width:1pt medium medium;padding:3pt 0cm 0cm;border-color:currentcolor"> <p class="MsoNormal" style="margin-bottom:12pt;margin-left:72pt"> <b><span style="font-size:12pt;color:black">From: </span></b><span style="font-size:12pt;color:black"><a href="mailto:cp2k@googlegroups.com" target="_blank">cp2k@googlegroups.com</a> <<a href="mailto:cp2k@googlegroups.com" target="_blank">cp2k@googlegroups.com</a>> on behalf of Victor Volkov <<a href="mailto:volkovskr@gmail.com" target="_blank">volkovskr@gmail.com</a>><br> <b>Date: </b>Saturday, 15 October 2022 at 19:53<br> <b>To: </b>cp2k <<a href="mailto:cp2k@googlegroups.com" target="_blank">cp2k@googlegroups.com</a>><br> <b>Subject: </b>[CP2K:17873] understanding BSSE print out</span><span style="font-size:11pt"><u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">Dear members:<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">good evening/morning.<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">it is not clear to me how to interpret CP2K print out for BSSE.<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">If I take a small guest (like benzene) next to a carbon layer using GWP/PBE/DZVP<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">Of course, since interactions are so week, DFTD3 is a must - otherwise a benzene may "fly away".<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">Then, using BSSE for S1(guest) and S2 (carbon layer)<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">CP2K prints<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">S1 + S2ghost: Total energy -455.12112693238430 Hartree<br> S1ghost + S2: Total energy -455.12112693238430 Hartree<br> S1 + S2: Total energy -455.12112693238441 Hartree<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">The differences are none or tiny.<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">However, the final print is:<u></u><u></u></span></p> </div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">CP-corrected Total energy: 0.015729 <br> 1-body contribution: -44.96634268204556 <br> 1-body contribution: -410.13905550190344<br> 2-body contribution: 455.121127 <br> BSSE-free interaction energy: 455.121127<u></u><u></u></span></p> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <b><span style="font-size:11pt">First, it is not clear what is "CP".</span></b><span style="font-size:11pt"><u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">Next, i<b>f this is the value of the BSSE artifact</b> (due to the wave-function truncation), <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">then <b>its huge</b> 41.2964895 kJ/mole.<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">This would be <b>almost twice larger than the binding energy</b> of benzene-like guests when at carbonaceous surfaces.<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">This would mean that quality evaluations of binding energies for such systems using CP2K would be very difficult. <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">Any comments to hear would be nice.<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">Finally, it is not clear why 2-body contribution and<b> BSSE-free interaction are printed as positive numbers</b>.<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">I hope the questions I ask be interesting for users and helpful for the on-line manual to update.<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">After all, I wish to note that it was by a <b>rare chance I was able to track</b> the old <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">notice <b>on the importance of declaring</b><u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> &KIND X_ghost<br> BASIS_SET DZVP-MOLOPT-SR-GTH<br> GHOST<br> &END KIND <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">Even though ... <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <b><span style="font-size:11pt">if I skip such definition, the numbers would come "a bit better"</span></b><span style="font-size:11pt"><u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <b><span style="font-size:11pt">:-)</span></b><span style="font-size:11pt"><u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">CP would be about 21 kJ/mole, what is about comparable to the binding energy <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">of a benzene-like guest to a carbonaceous material. <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">Thank you for your time and attention.<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt">I wish everybody be well and happy.<u></u><u></u></span></p> </div> <div> <p class="MsoNormal" style="margin-left:72pt"> <span style="font-size:11pt"> <u></u><u></u></span></p> </div> <div> <p class="MsoNormal" 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