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<p><font face="Calibri">Dear Molpro folks,</font></p>
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<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
</font><sub><font face="Calibri" size="2">neutral at optimized anion geometry</font></sub><font face="Calibri">
</font><span style="margin:0px; font-family:"MS Mincho"">–</span><font face="Calibri"> E
</font><sub><font face="Calibri" size="2">optimized anion</font></sub><font face="Calibri">). I start with FeS- as a test firstly.
</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">The following is my input file:</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">***,FeS-</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri"> </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">memory,400,M</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">gprint</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">symmetry,nosym </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">geometry={</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">2</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">FeS</font></p>
<p style="margin:0px 0px 13px"><span style="margin:0px"><font face="Calibri"> </font></span><font face="Calibri">Fe</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">-0.33994333</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">0.04249292</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">0.00000000</font></p>
<p style="margin:0px 0px 13px"><span style="margin:0px"><font face="Calibri"> </font></span><font face="Calibri">S</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">1.83005667</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">0.04249292</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">0.00000000</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">}</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri"> </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">basis=TZVP</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri"> </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">{uhf</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">wf,spin=3,charge=-1}</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">optg</font><span style="margin:0px"><font face="Calibri">
</font></span><span style="margin:0px"><font face="Calibri"> </font></span><font face="Calibri">!geometry optimization of quartet anion FeS</font><sup><font face="Calibri" size="2">-</font></sup><font face="Calibri"> using hf</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">{uhf</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">wf,spin=2,charge=0}</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">!single point energy of triplet neutral FeS with above optimized geometry of quartet anion FeS</font><sup><font face="Calibri" size="2">-</font></sup><font face="Calibri"> using hf</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">{uhf</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">wf,spin=4,charge=0}</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">!single point energy of quintet neutral FeS with above optimized geometry of quartet anion FeS</font><sup><font face="Calibri" size="2">-</font></sup><font face="Calibri"> using hf</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri"> </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">---</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri"> </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">The result I obtained is:</font></p>
<p style="margin:0px 0px 13px"><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">UHF-SCF</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">UHF-SCF</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">OPTG(UHF)</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">UHF-SCF </font></p>
<p style="margin:0px 0px 13px"><span style="margin:0px"><font face="Calibri"> </font>
</span><font face="Calibri">-1659.77314480</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">-1659.70612062</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">-1659.86274040</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">-1659.85196075</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri"> </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">Thus, I can obtain the VDE = -1659.77314480</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">- (-1659.86274040) = 0.0895956 Hartree = 2.438 eV.</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri"> </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">And then, I did the same thing using B3lyp and TZVP.</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">The input:</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">***,FeS-</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri"> </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">memory,400,M</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">gprint</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">symmetry,nosym </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">geometry={</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">2</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">FeS</font></p>
<p style="margin:0px 0px 13px"><span style="margin:0px"><font face="Calibri"> </font></span><font face="Calibri">Fe</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">-0.33994333</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">0.04249292</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">0.00000000</font></p>
<p style="margin:0px 0px 13px"><span style="margin:0px"><font face="Calibri"> </font></span><font face="Calibri">S</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">1.83005667</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">0.04249292</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">0.00000000</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">}</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri"> </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">basis=TZVP</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri"> </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">{uks,b3lyp</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">wf,spin=3,charge=-1}</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">optg</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">{uks,b3lyp</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">wf,spin=2,charge=0}</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">{uks,b3lyp</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">wf,spin=4,charge=0}</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">---</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">The results:</font></p>
<p style="margin:0px 0px 13px"><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">UKS-SCF</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">UKS-SCF</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">OPTG(UKS)</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">UKS-SCF </font></p>
<p style="margin:0px 0px 13px"><span style="margin:0px"><font face="Calibri"> </font>
</span><font face="Calibri">-1661.78663123</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">-1661.76503538</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">-1661.76845789</font><span style="margin:0px"><font face="Calibri">
</font></span><font face="Calibri">-1661.76799811</font></p>
<p style="margin:0px 0px 13px"><br>
</p>
<p style="margin:0px 0px 13px"><font face="Calibri">Thus, I can obtain the VDE = -1661.78663123</font><span style="margin:0px"><font face="Calibri">
</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">
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<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>
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<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">
<p align="center" style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">Molpro</font></p>
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<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">
<p align="center" style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">Gaussian</font></p>
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<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>
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<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">
<p align="center" style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">hf/TZVP</font></p>
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<p align="center" style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">B3lyp/TZVP</font></p>
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<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">
<p align="center" style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">hf/TZVP</font></p>
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<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">
<p align="center" style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">B3lyp/TZVP</font></p>
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<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">Calculated VDE of quartet anion FeS</font><sup><font face="Calibri" size="2">-</font></sup><font face="Calibri"> (ground state)</font></p>
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<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">
<p align="center" style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">2.438 eV</font></p>
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<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">
<p align="center" style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">-0.494 eV</font></p>
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<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">
<p align="center" style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">0.83 eV</font></p>
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<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">
<p align="center" style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">1.43 eV</font></p>
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<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">Experimental VDE of anion FeS</font><sup><font face="Calibri" size="2">-</font></sup></p>
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<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">
<p align="center" style="margin:0px; text-align:center; line-height:normal"><font face="Calibri">1.85 eV</font></p>
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</table>
<p style="margin:0px 0px 13px"><font face="Calibri"> </font></p>
<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>
<p style="margin:0px 0px 13px"><font face="Calibri"> </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">Best regards,</font></p>
<p style="margin:0px 0px 13px"><font face="Calibri"> </font></p>
<p style="margin:0px 0px 13px"><font face="Calibri">Shi Yin </font><span style="margin:0px"><font face="Calibri"> </font></span></p>
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<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>
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