<html>
<head>
<meta http-equiv="Content-Type" content="text/html; charset=iso-8859-1">
<style type="text/css" style="display:none;"><!-- P {margin-top:0;margin-bottom:0;} --></style>
</head>
<body dir="ltr">
<div id="divtagdefaultwrapper" style="font-size:12pt;color:#000000;font-family:Calibri,Arial,Helvetica,sans-serif;" dir="ltr">
<p></p>
<div style="margin-top:0;margin-bottom:0;">Hello Kirk,</div>
<div style="margin-top:0;margin-bottom:0;">Thanks a lot for your reply and suggestions. I tried what you suggested. The input and output files are attached.</div>
<div style="margin-top:0;margin-bottom:0;">(1) print orbitals and inspect results. I think Molpro has converged to the correct electronic states.
</div>
<div style="margin-top:0;margin-bottom:0;">(2) specify the occupied and closed orbitals. </div>
<div style="margin-top:0;margin-bottom:0;">(3) use b3lyp3 in Molpro.</div>
<div style="margin-top:0;margin-bottom:0;">I still get a negative VDE (-1661.94986404-(-1661.93508265)=-0.01478139).</div>
<div style="margin-top:0;margin-bottom:0;"> </div>
<div> UKS-SCF UKS-SCF OPTG(UKS) <br>
-1661.94986404 -1661.92823332 -1661.93508265 </div>
<div><br>
</div>
<div>Is there anything wrong of my input (see below), which part I try to calculate the single point energy of the neutral cluster which with the same optg structure of ion?</div>
<div>
<div><br>
</div>
<div>{uks,b3lyp3<br>
occ,22<br>
closed,20<br>
wf,42,1,2<br>
}</div>
<div>{uks,b3lyp3<br>
occ,23<br>
closed,19<br>
wf,42,1,4<br>
}</div>
<div><br>
</div>
<div>Thanks a lot for your help! </div>
</div>
<div><br>
</div>
<div>Shi</div>
<br>
<p></p>
<p><br>
</p>
<div id="Signature">
<div id="divtagdefaultwrapper" style="color:rgb(0,0,0); font-family:Calibri,Arial,Helvetica,sans-serif; font-size:12pt; background-color:rgb(255,255,255)">
<div style="font-family:Tahoma; font-size:13px"><span class="sig">-- <br>
Shi Yin</span></div>
<div style="font-family:Tahoma; font-size:13px"><span class="sig">Web site: <a class="OWAAutoLink" id="LPNoLP" href="http://sites.chem.colostate.edu/bernsteinlab/SY.htm">
http://sites.chem.colostate.edu/bernsteinlab/SY.htm</a><br>
Department of Chemistry<br>
Colorado State University<br>
Fort Collins, CO 80523<br>
Phone Numbers: Office 970-491-5741; Lab -5787</span></div>
</div>
</div>
<br>
<br>
<div style="color: rgb(0, 0, 0);">
<hr tabindex="-1" style="display:inline-block; width:98%">
<div id="divRplyFwdMsg" dir="ltr"><font color="#000000" face="Calibri, sans-serif" style="font-size:11pt"><b>From:</b> Peterson, Kirk <kipeters@wsu.edu><br>
<b>Sent:</b> Wednesday, December 7, 2016 9:56 AM<br>
<b>To:</b> Yin,Shi<br>
<b>Cc:</b> molpro-user molpro-user<br>
<b>Subject:</b> Re: [molpro-user] Ask help on molpro calculation as a new user</font>
<div> </div>
</div>
<div>Dear Shi Yin,
<div><br>
</div>
<div>you should make sure to print your orbitals and closely inspect your results to make sure Molpro has converged to the correct electronic states. You probably have to explicitly specify the occupied and closed orbitals. Note also that the default implementation
of B3LYP in Molpro is slightly different from that in Gaussian. I believe you should use b3lyp3 in Molpro.</div>
<div><br>
</div>
<div>best,</div>
<div><br>
</div>
<div>-Kirk</div>
<div><br>
<div>
<blockquote type="cite">
<div>On Dec 7, 2016, at 8:32 AM, Yin,Shi <<a href="mailto:Shi.Yin@colostate.edu">Shi.Yin@colostate.edu</a>> wrote:</div>
<br class="Apple-interchange-newline">
<div>
<div id="divtagdefaultwrapper" style="font-style:normal; font-weight:normal; letter-spacing:normal; orphans:auto; text-align:start; text-indent:0px; text-transform:none; white-space:normal; widows:auto; word-spacing:0px; font-size:12pt; font-family:Calibri,Arial,Helvetica,sans-serif" dir="ltr">
<div style="margin-top:0px; margin-bottom:0px"><font face="Calibri">Dear Molpro folks,</font></div>
<div>
<div>
<div id="divtagdefaultwrapper" style="font-size:12pt; font-family:Calibri,Arial,Helvetica,sans-serif" dir="ltr">
<div>
<p style="margin:0px 0px 13px"><font face="Calibri">I am, Shi Yin, working in Prof. Elliot Bernstein group, Chemistry department at Colorado State University. Recently, I start to use molpro to do calculation on iron sulfur negative ion clusters.</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">I am trying to do calculations of their theoretical first vertical detachment energies (VDE = E<span class="Apple-converted-space"> </span></font><sub><font face="Calibri" size="2">neutral at optimized anion
geometry</font></sub><font face="Calibri"><span class="Apple-converted-space"> </span></font><span style="margin:0px; font-family:'MS Mincho'">–</span><font face="Calibri"><span class="Apple-converted-space"> </span>E<span class="Apple-converted-space"> </span></font><sub><font face="Calibri" size="2">optimized
anion</font></sub><font face="Calibri">). I start with FeS- as a test firstly.</font><font face="Calibri">I can obtain the VDE = -1661.78663123</font><span style="margin:0px"><font face="Calibri"> <span class="Apple-converted-space"> </span></font></span><font face="Calibri">-
(-1661.76845789) = -0.01817334 Hartree = -0.494 eV.</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">Because I used Gaussian previously, I compared obtained results with Gaussian, and experimental results, as listed in the following table.</font></p>
<table style="margin:0px; border:medium; border-collapse:collapse" border="1" cellspacing="0" cellpadding="0">
<tbody>
<tr>
<td width="177" valign="top" style="margin:0px; padding:0in 5.4pt; border:1px solid rgb(0,0,0); width:88.55pt; background-color:transparent">
<p style="margin:0px; line-height:normal"><font face="Calibri"> </font></p>
</td>
<td width="354" valign="top" style="border-width:1px 1px 1px 0px; border-style:solid solid solid none; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:177.1pt; background-color:transparent" colspan="2">
<div style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">Molpro</font></div>
</td>
<td width="354" valign="top" style="border-width:1px 1px 1px 0px; border-style:solid solid solid none; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:177.15pt; background-color:transparent" colspan="2">
<div style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">Gaussian</font></div>
</td>
</tr>
<tr>
<td width="177" valign="top" style="border-width:0px 1px 1px; border-style:none solid solid; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:88.55pt; background-color:transparent">
<p style="margin:0px; line-height:normal"><font face="Calibri"> </font></p>
</td>
<td width="177" valign="top" style="border-width:0px 1px 1px 0px; border-style:none solid solid none; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:88.55pt; background-color:transparent">
<div style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">hf/TZVP</font></div>
</td>
<td width="177" valign="top" style="border-width:0px 1px 1px 0px; border-style:none solid solid none; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:88.55pt; background-color:transparent">
<div style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">B3lyp/TZVP</font></div>
</td>
<td width="177" valign="top" style="border-width:0px 1px 1px 0px; border-style:none solid solid none; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:88.55pt; background-color:transparent">
<div style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">hf/TZVP</font></div>
</td>
<td width="177" valign="top" style="border-width:0px 1px 1px 0px; border-style:none solid solid none; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:88.6pt; background-color:transparent">
<div style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">B3lyp/TZVP</font></div>
</td>
</tr>
<tr>
<td width="177" valign="top" style="border-width:0px 1px 1px; border-style:none solid solid; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:88.55pt; background-color:transparent">
<div style="margin:0px; line-height:normal"><font face="Calibri">Calculated VDE of quartet anion FeS</font><sup><font face="Calibri" size="2">-</font></sup><font face="Calibri">(ground state)</font></div>
</td>
<td width="177" valign="top" style="border-width:0px 1px 1px 0px; border-style:none solid solid none; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:88.55pt; background-color:transparent">
<div style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">2.438 eV</font></div>
</td>
<td width="177" valign="top" style="border-width:0px 1px 1px 0px; border-style:none solid solid none; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:88.55pt; background-color:transparent">
<div style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">-0.494 eV</font></div>
</td>
<td width="177" valign="top" style="border-width:0px 1px 1px 0px; border-style:none solid solid none; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:88.55pt; background-color:transparent">
<div style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">0.83 eV</font></div>
</td>
<td width="177" valign="top" style="border-width:0px 1px 1px 0px; border-style:none solid solid none; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:88.6pt; background-color:transparent">
<div style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">1.43 eV</font></div>
</td>
</tr>
<tr>
<td width="177" valign="top" style="border-width:0px 1px 1px; border-style:none solid solid; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:88.55pt; background-color:transparent">
<div style="margin:0px; line-height:normal"><font face="Calibri">Experimental VDE of anion FeS</font><sup><font face="Calibri" size="2">-</font></sup></div>
</td>
<td width="709" valign="top" style="border-width:0px 1px 1px 0px; border-style:none solid solid none; border-color:rgb(0,0,0); margin:0px; padding:0in 5.4pt; width:354.25pt; background-color:transparent" colspan="4">
<div style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">1.85 eV</font></div>
</td>
</tr>
</tbody>
</table>
<div style="margin:0px 0px 13px"><font face="Calibri"> </font><br class="webkit-block-placeholder">
</div>
<p style="margin:0px 0px 13px"><font face="Calibri">I am confused, because the results obtained by Molpro are very different with that obtained by Gaussian, and the Gaussian results seems more reasonable comparing with the experimental result.</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">Since I am a new user of Molpro, I am not sure my Molpro calculations are right or not. Could someone help me to check my input file to see if there is any problem or mistake?</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">Or please feel free to let me know any comments and suggestions to understand the above results listed in the table.</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">I will appreciate your reply and help very much!</font></p>
<div style="margin:0px 0px 13px"><font face="Calibri"> </font><br class="webkit-block-placeholder">
</div>
<p style="margin:0px 0px 13px"><font face="Calibri">Best regards,</font></p>
<div style="margin:0px 0px 13px"><font face="Calibri"> </font><br class="webkit-block-placeholder">
</div>
<p style="margin:0px 0px 13px"><font face="Calibri">Shi Yin<span class="Apple-converted-space"> </span></font></p>
</div>
<div id="Signature"></div>
</div>
</div>
</div>
</div>
</div>
</blockquote>
</div>
<br>
</div>
</div>
</div>
</div>
</body>
</html>