<html><head><meta http-equiv="Content-Type" content="text/html; charset=utf-8"></head><body style="word-wrap: break-word; -webkit-nbsp-mode: space; line-break: after-white-space;" class="">Dear Jan, <div class=""><br class=""></div><div class="">thanks for putting this to our attention, the deviation looks indeed on the upper end. </div><div class="">However, computing numerical derivatives is a bit tricky and has to be done with </div><div class="">maximum accuracy, since relative deviations of small values are reported. </div><div class="">So this may be an error, but can you please increase EPS_DEFAULT to 10E-16 </div><div class="">and EPS_SCF to 10E-7 and try this also with DX to 5.0E-4? </div><div class=""><br class=""></div><div class="">Cheers, </div><div class="">Thomas</div><div class=""><br class=""></div><div class="">P.S. BTW, I did a similar test with the sole PADE XC functional, which is supposed </div><div class="">to mimic PW92 LDA many years ago and it passed the test ...<br class=""><div><br class=""><blockquote type="cite" class=""><div class="">Am 30.04.2020 um 17:30 schrieb Jan Elsner <<a href="mailto:janel...@gmail.com" class="">janel...@gmail.com</a>>:</div><br class="Apple-interchange-newline"><div class=""><div dir="ltr" style="caret-color: rgb(0, 0, 0); font-family: Helvetica; font-size: 12px; font-style: normal; font-variant-caps: normal; font-weight: normal; letter-spacing: normal; text-align: start; text-indent: 0px; text-transform: none; white-space: normal; word-spacing: 0px; -webkit-text-stroke-width: 0px; text-decoration: none;" class=""><div class="">Dear all, </div><div class=""><br class=""></div><div class="">I thought I should post an update on this. </div><div class=""><br class=""></div><div class="">It seems that there is a problem with using PW92 as the local correlation part of XC functional. When I use VWN instead, the analytical and numerical forces are equal. I attach input and output files for DEBUG runs on a single H20 molecule using optPBE in combination with PW92 and VWN. In the case of PW92, there is a mismatch between analytical and numerical forces. </div><div class=""><br class=""></div><div class="">I note that the same applies for the some of the other functionals listed here: <a href="https://github.com/cp2k/cp2k/tree/master/data/xc_section" class="">https://github.com/cp2k/cp2k/tree/master/data/xc_section</a> (at least, I can confirm that optB88 and C09 also give a mismatch between numerical and analytical forces using the settings listed here). </div><div class=""><br class=""></div><div class="">Best wishes, </div><div class=""><br class=""></div><div class="">Jan</div><div class=""><br class=""></div><div class=""><br class=""></div><br class=""><br class="">On Friday, April 24, 2020 at 10:43:00 AM UTC+1, Jan Elsner wrote:<blockquote class="gmail_quote" style="margin: 0px 0px 0px 0.8ex; border-left-width: 1px; border-left-style: solid; border-left-color: rgb(204, 204, 204); padding-left: 1ex;"><div dir="ltr" class="">Dear Juerg, <div class=""><br class=""></div><div class="">Many thanks for the quick response! Unfortunately, decreasing EPS_SCF (all the way to 1.0E-10) does not solve the problem. </div><div class=""><br class=""></div><div class="">I have done a DEBUG run which results in the following error (see end of attached file debug.out):<span class="Apple-converted-space"> </span><b class="">'Abort: A mismatch between the analytical and the numerical stress tensor has been detected. Check the implementation of the stress tensor'</b>. I'm not entirely sure how I should proceed from here / what the problem is exactly - any insight would be very much appreciated. </div><div class=""><br class=""></div><div class="">If it helps shed some light on the problem, I also attach a figure showing Total Energy, RMS Gradient and Cell Volume as a function of optimization step (plotted from the original cell.out file I sent). The optimiser seems to overshoot the minimum energy configuration. </div><div class=""><br class=""></div><div class="">One other question which comes to mind is whether it's ok to use GTH-PBE or GTH-PADE pseudopotentials with optPBE-vdW?</div><div class=""><br class=""></div><div class="">Best wishes, <br class=""><br class="">Jan</div><div class=""><br class=""></div><div class=""><br class=""></div><div class=""><br class=""></div><div class=""><br class=""><br class="">On Monday, April 20, 2020 at 10:20:34 AM UTC+1, jgh wrote:<blockquote class="gmail_quote" style="margin: 0px 0px 0px 0.8ex; border-left-width: 1px; border-left-style: solid; border-left-color: rgb(204, 204, 204); padding-left: 1ex;">Hi<span class="Apple-converted-space"> </span><br class=""><br class="">I don't know how well a setup as this is tested. However, from<span class="Apple-converted-space"> </span><br class="">your output I would guess the problem could be related to your<span class="Apple-converted-space"> </span><br class="">SCF convergence. With the methods you are using you have to set<span class="Apple-converted-space"> </span><br class="">the convergence criteria much tighter in order to get converged<span class="Apple-converted-space"> </span><br class="">energy and forces. I would suggest to use at least 1.E-8.<span class="Apple-converted-space"> </span><br class=""><br class="">The ultimate test would be to do a DEBUG run in order to verify<span class="Apple-converted-space"> </span><br class="">forces and stress tensor for the setting of options.<span class="Apple-converted-space"> </span><br class=""><br class="">regards<span class="Apple-converted-space"> </span><br class=""><br class="">Juerg Hutter<span class="Apple-converted-space"> </span><br class="">------------------------------<wbr class="">------------------------------<wbr class="">--<span class="Apple-converted-space"> </span><br class="">Juerg Hutter Phone : ++41 44 635 4491<span class="Apple-converted-space"> </span><br class="">Institut für Chemie C FAX : ++41 44 635 6838<span class="Apple-converted-space"> </span><br class="">Universität Zürich E-mail:<span class="Apple-converted-space"> </span><a rel="nofollow" class="">h...@chem.uzh.ch</a><span class="Apple-converted-space"> </span><br class="">Winterthurerstrasse 190<span class="Apple-converted-space"> </span><br class="">CH-8057 Zürich, Switzerland<span class="Apple-converted-space"> </span><br class="">------------------------------<wbr class="">------------------------------<wbr class="">---<span class="Apple-converted-space"> </span><br class=""><br class="">-----<a rel="nofollow" class="">c...@googlegroups.com</a><span class="Apple-converted-space"> </span>wrote: -----<span class="Apple-converted-space"> </span><br class="">To: "cp2k" <<a rel="nofollow" class="">c...@googlegroups.com</a>><span class="Apple-converted-space"> </span><br class="">From: "Jan Elsner"<span class="Apple-converted-space"> </span><br class="">Sent by:<span class="Apple-converted-space"> </span><a rel="nofollow" class="">c...@googlegroups.com</a><span class="Apple-converted-space"> </span><br class="">Date: 04/18/2020 08:33PM<span class="Apple-converted-space"> </span><br class="">Subject: [CP2K:13145] CELL Optimization - Energy not decreasing<span class="Apple-converted-space"> </span><br class=""><br class="">Dear all,<span class="Apple-converted-space"> </span><br class=""><br class="">I am trying to run a Cell Optimisation on a periodic molecular crystal (beta-resorcinol: C6H6O2, 4 molecules in unit cell) using K-points and BFGS as optimiser. I am using the vdW-DF-optPBE functional (<a href="https://github.com/cp2k/cp2k/commit/74ef05b96a46523a0daf7da04e75804420b5cd5e" rel="nofollow" target="_blank" class="">https://github.com/cp2k/cp2k/<wbr class="">commit/<wbr class="">74ef05b96a46523a0daf7da04e7580<wbr class="">4420b5cd5e</a>). After 83 optimisation steps, my system does converge to the required MOTION thresholds, however from step 7 onwards the total energy increases at every step i.e.:<span class="Apple-converted-space"> </span><br class=""><br class="">-------- Informations at step = 7 ------------<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Optimization Method = BFGS<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Total Energy = -280.1489665596<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Internal Pressure [bar] = -2667.4573178334<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Real energy change = 0.0001037473<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Predicted change in energy = -0.0001063956<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Scaling factor = 0.0000000000<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Step size = 0.0124910496<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Trust radius = 0.4724315332<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Decrease in energy = NO<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Used time = 60.978<span class="Apple-converted-space"> </span><br class=""><br class=""> <span class="Apple-converted-space"> </span>Convergence check :<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Max. step size = 0.0124910496<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Conv. limit for step size = 0.0010000000<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Convergence in step size = NO<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>RMS step size = 0.0029192108<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Conv. limit for RMS step = 0.0010000000<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Convergence in RMS step = NO<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Max. gradient = 0.0034738629<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Conv. limit for gradients = 0.0001000000<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Conv. for gradients = NO<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>RMS gradient = 0.0006857738<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Conv. limit for RMS grad. = 0.0001000000<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Conv. for gradients = NO<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Pressure Deviation [bar] = -2668.4705678334<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Pressure Tolerance [bar] = 200.0000000000<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>Conv. for PRESSURE = NO<span class="Apple-converted-space"> </span><br class=""> -----------------------------<wbr class="">----------------------<span class="Apple-converted-space"> </span><br class=""><br class="">The resulting cell-optimised structure is therefore not a minimum in energy. I've attached the input and output files. Some points which may (or may not) be relevant:<span class="Apple-converted-space"> </span><br class="">I did not encounter this problem when using a different functional (PBE + D3 instead of optPBE-vdW as used here), but otherwise identical settings.<span class="Apple-converted-space"> </span><br class="">I encountered the same issue (energy increasing at every step) using CUTOFF/REL_CUTOFF = 800/60<span class="Apple-converted-space"> </span><br class="">I initially tried to converge CUTOFF and REL_CUTOFF as in the tutorial (<span class="Apple-converted-space"> </span><br class=""><a href="https://www.cp2k.org/howto:converging_cutoff" rel="nofollow" target="_blank" class="">https://www.cp2k.org/howto:<wbr class="">converging_cutoff</a>), however my single point calculations did not converge quite as nicely as in the tutorial - instead oscillating with an amplitude of order ~ e-4 Ha (I've attached a figure showing this). This is why I use such large CUTOFF/REL_CUTOFF values. I note that this was also the case when I ran PBE + D3 calculations, however in the latter case my cell optimisation did work.<span class="Apple-converted-space"> </span><br class=""><br class="">Any input would be greatly appreciated.<span class="Apple-converted-space"> </span><br class=""><br class="">Best wishes,<span class="Apple-converted-space"> </span><br class=""><br class="">Jan<span class="Apple-converted-space"> </span><br class=""><br class=""><br class=""> <span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span>--<span class="Apple-converted-space"> </span><br class=""> You received this message because you are subscribed to the Google Groups "cp2k" group.<span class="Apple-converted-space"> </span><br class=""> To unsubscribe from this group and stop receiving emails from it, send an email to<span class="Apple-converted-space"> </span><a rel="nofollow" class="">c...@googlegroups.com</a>.<span class="Apple-converted-space"> </span><br class=""> To view this discussion on the web visit<span class="Apple-converted-space"> </span><a href="https://groups.google.com/d/msgid/cp2k/e97788c6-1c43-453d-893e-6b973a977f9d%40googlegroups.com" rel="nofollow" target="_blank" class="">https://groups.google.com/d/<wbr class="">msgid/cp2k/e97788c6-1c43-453d-<wbr class="">893e-6b973a977f9d%<wbr class="">40googlegroups.com</a>.<span class="Apple-converted-space"> </span><br class=""> <span class="Apple-converted-space"> </span><br class=""><br class="">[attachment "cell.inp" removed by Jürg Hutter/at/UZH]<span class="Apple-converted-space"> </span><br class="">[attachment "cell.out" removed by Jürg Hutter/at/UZH]<span class="Apple-converted-space"> </span><br class="">[attachment "E_vs_cutoff.png" removed by Jürg Hutter/at/UZH]<span class="Apple-converted-space"> </span><br class="">[attachment "subsys.include" removed by Jürg Hutter/at/UZH]<span class="Apple-converted-space"> </span><br class=""></blockquote></div></div></blockquote></div><div style="caret-color: rgb(0, 0, 0); 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text-transform: none; white-space: normal; word-spacing: 0px; -webkit-text-stroke-width: 0px; text-decoration: none;" class=""><span id="cid:5b66ce47-fb7b-4a1c-9f15-2a604316aa25"><pw92.inp></span><span id="cid:faeba783-00d2-45f3-a700-f6fcc580d8df"><pw92.out></span><span id="cid:c57877f1-2c70-4ead-b1f3-6c934567c070"><vwn.inp></span><span id="cid:976812d9-0989-4c4d-adc7-58657f1d6bb8"><vwn.out></span></div></blockquote></div><br class=""></div><br class=""><br class=""><div class=""> <div style="color: rgb(0, 0, 0); letter-spacing: normal; text-align: start; text-indent: 0px; text-transform: none; white-space: normal; word-spacing: 0px; -webkit-text-stroke-width: 0px; word-wrap: break-word; -webkit-nbsp-mode: space; -webkit-line-break: after-white-space;" class=""><div style="color: rgb(0, 0, 0); letter-spacing: normal; text-align: start; text-indent: 0px; text-transform: none; white-space: normal; word-spacing: 0px; -webkit-text-stroke-width: 0px; word-wrap: break-word; -webkit-nbsp-mode: space; 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font-variant-position: normal; font-weight: normal; letter-spacing: normal; line-height: normal; text-align: start; text-indent: 0px; text-transform: none; white-space: normal; word-spacing: 0px; -webkit-text-stroke-width: 0px; orphans: 2; widows: 2;" class="">Thomas D. 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