<html><head></head><body><div style="color:#000; background-color:#fff; font-family:標楷體, dfkai-sb;font-size:16px"><div id="yui_3_16_0_ym19_1_1502858306704_6729">Dear Tatiana,</div><div id="yui_3_16_0_ym19_1_1502858306704_6730"><br id="yui_3_16_0_ym19_1_1502858306704_6731"></div><div id="yui_3_16_0_ym19_1_1502858306704_6732">thank you for your reply. </div><div id="yui_3_16_0_ym19_1_1502858306704_6733">I forgot to put "variable, energy(2);" in the frequency card.</div><div id="yui_3_16_0_ym19_1_1502858306704_6733"><br></div><div id="yui_3_16_0_ym19_1_1502858306704_6733">As I understand, it is expected that the optimization results <br></div><div id="yui_3_16_0_ym19_1_1502858306704_6737">are different if different point groups were chosen? </div><div id="yui_3_16_0_ym19_1_1502858306704_6738"><br></div><div id="yui_3_16_0_ym19_1_1502858306704_6738">For 2.2 state I experienced the following problems. <br></div><div id="yui_3_16_0_ym19_1_1502858306704_6741">Molpro chooses the C2v symmetry for H2O for optimization by default.</div><div id="yui_3_16_0_ym19_1_1502858306704_6742">However, for freq calculations it chooses C1 group and then fails</div><div id="yui_3_16_0_ym19_1_1502858306704_6743">with the error: </div><div id="yui_3_16_0_ym19_1_1502858306704_6743"><br></div><div id="yui_3_16_0_ym19_1_1502858306704_6743"> ?ILLEGAL SYMMETRY ON EOM CARD: 2 </div><div id="yui_3_16_0_ym19_1_1502858306704_6743"><br></div><div id="yui_3_16_0_ym19_1_1502858306704_6743">If I force Molpro to use the C2v symmetry for freq calculations,</div><div id="yui_3_16_0_ym19_1_1502858306704_6750">then it fails with different error: </div><div id="yui_3_16_0_ym19_1_1502858306704_6751"> Attempt to include non-existent symmetry X <br></div><div id="yui_3_16_0_ym19_1_1502858306704_6754"> ...</div><div id="yui_3_16_0_ym19_1_1502858306704_6755"> ? The problem occurs in zmatrix.f:zmat_evaluate</div><div id="yui_3_16_0_ym19_1_1502858306704_6755"><br></div><div id="yui_3_16_0_ym19_1_1502858306704_6755">For 3.1 state C2v group works for freq analysis, but gives imaginary frequencies.</div><div id="yui_3_16_0_ym19_1_1502858306704_6760">It may be related to the fact that optimization for C2v group converges</div><div id="yui_3_16_0_ym19_1_1502858306704_6761">to a saddle point. </div><div id="yui_3_16_0_ym19_1_1502858306704_6761"><br></div><div id="yui_3_16_0_ym19_1_1502858306704_6761">The only successful way was when I chose the nosym option both for opt and freq analysis</div><div id="yui_3_16_0_ym19_1_1502858306704_6765">for 3.1 state, in this case I got real freqs and no warning about the gradient.</div><div id="yui_3_16_0_ym19_1_1502858306704_6766"><br></div><div id="yui_3_16_0_ym19_1_1502858306704_6766">Are these problems related to state degeneracies or some vibronic interactions?<br></div><div id="yui_3_16_0_ym19_1_1502858306704_6769"><br></div><div id="yui_3_16_0_ym19_1_1502858306704_6769">Saludos cordiales,</div><div id="yui_3_16_0_ym19_1_1502858306704_6648"></div><div dir="ltr" id="yui_3_16_0_ym19_1_1502858306704_6772">Pablo Avaria</div> <div class="qtdSeparateBR"><br><br></div><div class="yahoo_quoted" style="display: block;"> <div style="font-family: 標楷體, dfkai-sb; font-size: 16px;"> <div style="font-family: HelveticaNeue, Helvetica Neue, Helvetica, Arial, Lucida Grande, sans-serif; font-size: 16px;"> <div dir="ltr"><font size="2" face="Arial"> On Monday, August 14, 2017 6:29 AM, Tatiana Korona <tania@tiger.chem.uw.edu.pl> wrote:<br></font></div> <br><br> <div class="y_msg_container"><div dir="ltr">Dear Pablo,<br clear="none"><br clear="none">If you want frequencies for the 2.1 state, you should specify this explicitly, <br clear="none">otherwise they are calculated for the default (ground) state. You did it for the <br clear="none">optimization, but forgot to do the same for the frequency job.<br clear="none"><br clear="none">Best wishes,<br clear="none"><br clear="none">Tatiana<br clear="none"><div class="yqt3132283940" id="yqtfd30627"><br clear="none"> On Fri, 11 Aug 2017, Pablo Avaria wrote:<br clear="none"><br clear="none">> Hello,<br clear="none">><br clear="none">> I was trying to use EOM-CCSD for finding harmonic frequencies of H2O molecule for excited states. First, I optimized the geometry for 2.1 state, see first attachment.Then, I did freq analysis, see second attachment.<br clear="none">> However, it looks like that the freqs are calculated for a different electronic statethan was used for optimization.<br clear="none">> Optimization: Results for state 2.1: Excitation energy 0.36677468 au Freq: Results for state 2.1: Excitation energy 0.34742486 au Moreover, the freq output contains the line ?WARNING: GRADIENT NORM NOT ZERO! which confirms that the geometry used is not the equillibrium one. Should I set some parameters manually in the freq input?I suspect it is related to the symmetry somehow, but I don't know how to manage it. <br clear="none">> Regards,<br clear="none">> Pablo</div><br clear="none"><br clear="none">Dr. Tatiana Korona <a shape="rect" href="http://tiger.chem.uw.edu.pl/staff/tania/index.html" target="_blank">http://tiger.chem.uw.edu.pl/staff/tania/index.html</a><br clear="none">Quantum Chemistry Laboratory, University of Warsaw, Pasteura 1, PL-02-093 Warsaw, POLAND</div><br><br></div> </div> </div> </div></div></body></html>