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Dear Jan,<div><br></div><div>I can reproduce the G03 RHF energy (HF=-262.3384479) by using the "MULTI" command in Molpro. I've previously found this algorithm to converge more reliably for some systems, especially radical anions. Strangely, when I read the MCSCF (CSF=1) wave function into ROHF I continue to get the same (higher) energy you have found. </div><div><br></div><div>I'm certainly not a guru (and this doesn't really solve your problem, i.e., why isn't ROHF converging to the lower solution), but it may nonetheless be of some assistance.</div><div><br></div><div>With best wishes,</div><div>Greg</div><div><br></div><div><br></div><div><span class="Apple-style-span" style="font-weight: bold; ">INPUT:</span></div><div><br></div><div>memory,8,m</div><div>gthresh,energy=1d-12,twoint=1d-18,prefac=1d-20</div><div>geomtyp=xyz</div><div>geom={</div><div> 4</div><div>E(UHF)=-262.355671204 au|Dpl=(0.5152,-0.4848,0) D||E(ROHF)=-262.338447756 au|Dpl=(0.9471,-1.9519,0) Debye</div><div>O -0.832632 1.113558 0.000000</div><div>C 0.000000 0.281073 0.000000</div><div>O -0.367117 -1.293021 0.000000</div><div>O 1.199748 -0.031341 0.000000</div><div>}</div><div>basis=vdz</div><div>int</div><div>{uhf;wf,30,2,2;occ,13,3;closed,12,2}</div><div>! yields the correct energy</div><div>!UHF STATE 1.2 ENERGY -262.355671266903</div><div>!UHF STATE 1.2 DIPOLE MOMENT 0.20268671 -0.19074510 0.00000000</div><div>{multi;occ,13,3;closed,12,2;wf,30,2,2}</div><div>{hf;wf,30,2,2;occ,13,3;closed,12,2}</div><div>! yields a different energy, and dipole vector looks very different too </div><div>!RHF STATE 1.2 ENERGY -262.331395031327</div><div>!RHF STATE 1.2 DIPOLE MOMENT 0.10470623 -0.21621532 0.00000000</div><div> </div><div><br></div><div><b>SELECTED OUTPUT:</b></div><div><br></div><div><div>1PROGRAM * MULTI (Direct Multiconfiguration SCF) Authors: P.J. Knowles, H.-J. Werner (1984) S.T. Elbert (1988)</div><div><br></div><div><br></div><div> Number of closed-shell orbitals: 14 ( 12 2 )</div><div> Number of active orbitals: 2 ( 1 1 )</div><div> Number of external orbitals: 40 ( 27 13 )</div><div><br></div><div> State symmetry 1</div><div><br></div><div> Number of electrons: 2 Spin symmetry=Triplet Space symmetry=2</div><div> Number of states: 1</div><div> Number of CSFs: 1 (1 determinants, 1 intermediate states)</div><div><br></div></div><div><br></div><div><div> **********************************************************************************************************************************</div><div><br></div><div> RHF-SCF MULTI UHF-SCF </div><div> -262.33139503 -262.33844792 -262.35567127</div><div> **********************************************************************************************************************************</div><div><br></div></div><div><br><div> <span class="Apple-style-span" style="border-collapse: separate; color: rgb(0, 0, 0); font-family: Helvetica; font-size: 12px; font-style: normal; font-variant: normal; font-weight: normal; letter-spacing: normal; line-height: normal; orphans: 2; text-align: auto; text-indent: 0px; text-transform: none; white-space: normal; widows: 2; word-spacing: 0px; -webkit-border-horizontal-spacing: 0px; -webkit-border-vertical-spacing: 0px; -webkit-text-decorations-in-effect: none; -webkit-text-size-adjust: auto; -webkit-text-stroke-width: 0; "><span class="Apple-style-span" style="border-collapse: separate; color: rgb(0, 0, 0); font-family: Helvetica; font-size: 12px; font-style: normal; font-variant: normal; font-weight: normal; letter-spacing: normal; line-height: normal; orphans: 2; text-indent: 0px; text-transform: none; white-space: normal; widows: 2; word-spacing: 0px; -webkit-border-horizontal-spacing: 0px; -webkit-border-vertical-spacing: 0px; -webkit-text-decorations-in-effect: none; -webkit-text-size-adjust: auto; -webkit-text-stroke-width: 0px; "><span class="Apple-style-span" style="border-collapse: separate; -webkit-border-horizontal-spacing: 0px; -webkit-border-vertical-spacing: 0px; color: rgb(0, 0, 0); font-family: Helvetica; font-size: 12px; font-style: normal; font-variant: normal; font-weight: normal; letter-spacing: normal; line-height: normal; -webkit-text-decorations-in-effect: none; text-indent: 0px; -webkit-text-size-adjust: auto; text-transform: none; orphans: 2; white-space: normal; widows: 2; word-spacing: 0px; "><span class="Apple-style-span" style="border-collapse: separate; -webkit-border-horizontal-spacing: 0px; -webkit-border-vertical-spacing: 0px; color: rgb(0, 0, 0); font-family: Helvetica; font-size: 12px; font-style: normal; font-variant: normal; font-weight: normal; letter-spacing: normal; line-height: normal; -webkit-text-decorations-in-effect: none; text-indent: 0px; -webkit-text-size-adjust: auto; text-transform: none; orphans: 2; white-space: normal; widows: 2; word-spacing: 0px; "><span class="Apple-style-span" style="border-collapse: separate; -webkit-border-horizontal-spacing: 0px; -webkit-border-vertical-spacing: 0px; color: rgb(0, 0, 0); font-family: Helvetica; font-size: 12px; font-style: normal; font-variant: normal; font-weight: normal; letter-spacing: normal; line-height: normal; -webkit-text-decorations-in-effect: none; text-indent: 0px; -webkit-text-size-adjust: auto; text-transform: none; orphans: 2; white-space: normal; widows: 2; word-spacing: 0px; "><span class="Apple-style-span" style="border-collapse: separate; -webkit-border-horizontal-spacing: 0px; -webkit-border-vertical-spacing: 0px; color: rgb(0, 0, 0); font-family: Helvetica; font-size: 12px; font-style: normal; font-variant: normal; font-weight: normal; letter-spacing: normal; line-height: normal; -webkit-text-decorations-in-effect: none; text-indent: 0px; -webkit-text-size-adjust: auto; text-transform: none; orphans: 2; white-space: normal; widows: 2; word-spacing: 0px; "><span class="Apple-style-span" style="border-collapse: separate; -webkit-border-horizontal-spacing: 0px; -webkit-border-vertical-spacing: 0px; color: rgb(0, 0, 0); font-family: Helvetica; font-size: 12px; font-style: normal; font-variant: normal; font-weight: normal; letter-spacing: normal; line-height: normal; -webkit-text-decorations-in-effect: none; text-indent: 0px; -webkit-text-size-adjust: auto; text-transform: none; orphans: 2; white-space: normal; widows: 2; word-spacing: 0px; "><span class="Apple-style-span" style="border-collapse: separate; -webkit-border-horizontal-spacing: 0px; -webkit-border-vertical-spacing: 0px; color: rgb(0, 0, 0); font-family: Helvetica; font-size: 12px; font-style: normal; font-variant: normal; font-weight: normal; letter-spacing: normal; line-height: normal; -webkit-text-decorations-in-effect: none; text-indent: 0px; -webkit-text-size-adjust: auto; text-transform: none; orphans: 2; white-space: normal; widows: 2; word-spacing: 0px; "><div>***</div><div>Gregory M. Sandala, PhD</div><div>School of Chemistry, Bldg F11<span class="Apple-tab-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "> </span></span></span></span></span></span></div><div>University of Sydney<span class="Apple-tab-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "> </span></span></span></span></span></span></div><div><span class="Apple-style-span">NSW 2006<span class="Apple-style-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; ">, </span></span></span></span><span class="Apple-tab-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: pre; "><span class="Apple-style-span" style="white-space: normal; ">Australia</span></span></span></span></span></div>Ph: +61 2 9351 5361<br class="Apple-interchange-newline"></span><a href="mailto:sandala@chem.usyd.edu.au">sandala@chem.usyd.edu.au</a><br class="Apple-interchange-newline"></span></span></span></span></span></span></span> </div><br><div><div>On 27/04/2008, at 8:22 AM, Gershom (Jan M.L.) Martin wrote:</div><br class="Apple-interchange-newline"><blockquote type="cite">Dear MOLPRO gurus:<br><br>Very recently I ran into a peculiar example of a transition state for which MOLPRO disagrees with every other code on the ROHF reference energy. See the simple input below. I tried every SCF convergence acceleration/coaxing trick in the book and a few that aren't, to no avail.<br> <br>The other structures on the same PES do not exhibit the problem. Does anybody have a clue what I am overlooking?<br><br>(And yes, I know this is a highly multiref problem. Still, ROHF should give the same answer as Gaussian and ACES?)memory,8,m<br> <br>Many thanks in advance!<br>Jan Martin<br><br><br> 4<br>E(UHF)=-262.355671204 au|Dpl=(0.5152,-0.4848,0) D||E(ROHF)=-262.338447756 au|Dpl=(0.9471,-1.9519,0) Debye<br>O -0.832632 1.113558 0.000000<br>C 0.000000 0.281073 0.000000<br> O -0.367117 -1.293021 0.000000<br>O 1.199748 -0.031341 0.000000<br>}<br>basis=vdz<br>int<br>{uhf;wf,30,2,2;occ,13,3;closed,12,2}<br>! yields the correct energy<br>!UHF STATE 1.2 ENERGY -262.355671266903<br> !UHF STATE 1.2 DIPOLE MOMENT 0.20268671 -0.19074510 0.00000000<br>{hf;wf,30,2,2;occ,13,3;closed,12,2}<br>! yields a different energy, and dipole vector looks very different too <br>!RHF STATE 1.2 ENERGY -262.331395031327<br> !RHF STATE 1.2 DIPOLE MOMENT 0.10470623 -0.21621532 0.00000000<br><br><br></blockquote></div><br></div></body></html>