<html><body style="word-wrap: break-word; -webkit-nbsp-mode: space; -webkit-line-break: after-white-space; "><div><br></div>If you turn off symmetry, then both the A' and A" have symmetry A and you do have two states of the same symmetry. From the look of this output though it appears that state-averaged gradients only work with segmented basis sets which is not the newer program that can do analytical hessians. Your frequency calculation would then calculate the hessian by numerical differentiation of the analytical gradient (so disregard my cpmcscf,hess input).<div><br></div><div>So I would recommend going back to your original input (in symmetry), removing the 2nd cpmcscf card, and in the frequency command use: freq,central</div><div><br></div><div>-Kirk</div><div><br></div><div><br><div><div>On Oct 4, 2008, at 3:49 PM, Jayashree wrote:</div><br class="Apple-interchange-newline"><blockquote type="cite"><div dir="ltr">Two things -<br>1. I need to have a UHF input, since I am dealing with a doublet. <br>2. The present calculation is a conical intersection between A' and A" states. This is same as the conical intersection at the C3v geometry of methoxy molecule. In that case, I cannot have 2 states in the symmetry 1. <br> <br>But in any case, I tried the input given to me by you, and it terminates with the following message - (this is the section of output of MULTI program..the UHF and optg calculations run ok.<br>1PROGRAM * MULTI (Direct Multiconfiguration SCF) Authors: P.J. Knowles, H.-J. Werner (1984) S.T. Elbert (1988)<br> Number of closed-shell orbitals: 3 ( 3 )<br> Number of active orbitals: 6 ( 6 )<br> Number of external orbitals: 37 ( 37 )<br> State symmetry 1<br> Number of electrons: 11 Spin symmetry=Doublet Space symmetry=1<br> Number of states: 2<br> Number of CSFs: 6 (6 determinants, 6 intermediate states)<br> NOEXTRA OPTION SET FOR FREQUENCY CALCULATION<br> Molecular orbitals read from record 2200.2 Type=UHF/NATURAL (state 1.1)<br> Wavefunction dump at record 2140.2<br> Convergence thresholds 0.10E-05 (gradient) 0.10E-07 (energy) 0.10E-02 (step length)<br> Weight factors for state symmetry 1: 0.50000 0.50000<br> Number of orbital rotations: 351 ( 18 Core/Active 111 Core/Virtual 0 Active/Active 222 Active/Virtual)<br> Total number of variables: 363<br> ITER. MIC NCI NEG ENERGY(VAR) ENERGY(PROJ) ENERGY CHANGE GRAD(0) GRAD(ORB) GRAD(CI) STEP TIME<br> ?WARNING, SMALL DIAGONAL HESSIAN ELEMENT FOR ROTATION 3.1 - 4.1 D1E=-0.248D-06 D2E= 0.421D-07<br> ?WARNING, SMALL DIAGONAL HESSIAN ELEMENT FOR ROTATION 3.1 - 5.1 D1E=-0.632D-07 D2E= 0.135D-07<br> 1 60 7 0 -114.40430384 -114.40955138 -0.00524754 0.05457236 0.00064851 0.00000000 0.44D-01 0.35<br> ERROR EXIT<br> CURRENT STACK: MAIN<br> 2 201 15 0 -114.40957522 -114.40957745 -0.00000223 0.00273117 0.00003244 0.00000000 0.10D-02 1.03<br> 3 60 16 0 -114.40957745 -114.40957745 0.00000000 0.00003241 0.00000000 0.00000000 0.28D-04 1.56<br> ** WVFN **** CONVERGENCE REACHED, FINAL GRADIENT: 0.42D-09<br> CPMCSCF calculation required for state-averaged gradient calculation. Please add<br> CPMCSCF,GRAD,STATE=istate.isym<br> to the mcscf/casscf input, where istate.isym specifies the state for which the gradients are required.<br> Note that gradients for state-averaged MCSCF can only be computed with segmented basis sets.<br> For more details, please refer to the MOLPRO manual.<br> ? Error<br> ? Missing cpmcscf<br> ? The problem occurs in musave<br> -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------<br>If I use the following input indicating that the intersection is of states of different symmetry, it terminates with the following message -<br> NOEXTRA OPTION SET FOR FREQUENCY CALCULATION<br><br> ?STATE SYMMETRY NOT POSSIBLE: 2<br><br>My input looks like this - <br>basis=6-311++G<br>geomtype={zmat}<br>geometry={Angstrom;nosym<br> c;<br> o,c,oc;<br> h1,c,h1c,o,h1co;<br> h2,c,h1c,o,h1co,h1,120.0;<br> h3,c,h1c,o,h1co,h1,240.0}<br>oc=1.410000, h1c=1.100000, h1co=109.100000<br><br> {uhf} !uhf input without symmetry<br> put,molden,met_uhf_6311++g.molden<br> <br> {optg,space=zmat}<br> put,molden,met_opt_6311++g.molden<br><br> {casscf;<br> occ,9;<br> closed,3;<br> wf,17,1,1;<br> state,1;<br> weight,0.5<br> wf,17,2,1;<br> state,1;<br> weight,0.5<br> start,orbital=2200.2<br> <br> CPMCSCF,HESS}<br> {optg,startcmd=casscf}<br> put,molden,met_cas_6311++g_con.molden<br> {frequencies}<br><br>Any hope of calculating frequencies keeping symmetry in the input?<br>Thanks<br>Jayashree<br><br><div class="gmail_quote"> On Sat, Oct 4, 2008 at 11:21 AM, Kirk Peterson <span dir="ltr"><<a href="mailto:kipeters@wsu.edu">kipeters@wsu.edu</a>></span> wrote:<br><blockquote class="gmail_quote" style="border-left: 1px solid rgb(204, 204, 204); margin: 0pt 0pt 0pt 0.8ex; padding-left: 1ex;"> <div style="">The analytical MCSCF hessian calculation can only be performed without symmetry. I'm not sure about state-averaged wavefunctions, but you can try put a "nosym" in your geometry block after "Angstrom", comment out your rhf input, and then in your casscf input change this to something like:<div> <br></div><div> {casscf;<br> occ,9;<br> closed,3;<br> wf,17,1,1;<br> state,2;<br> CPMCSCF,HESS}</div><div><br></div><div><br></div><div>-Kirk</div><div><br><div><div><div></div><div class="Wj3C7c"><div>On Oct 3, 2008, at 1:18 PM, Jayashree wrote:</div> <br></div></div><blockquote type="cite"><div><div></div><div class="Wj3C7c"><div dir="ltr">I have located a conical intersection corresponding to the C3v geometry in methoxy molecule. I would like to calculate the normal mode frequencies of the molecule at this geometry. If I try to give the command 'frequencies' below 'optg', I get the following error: <br> ?STATE SYMMETRY NOT POSSIBLE: 2<br>How do I calculate the frequencies?<br><br>This is how my input file looks like - <br>***,methoxy <br>memory,128,m<br>file,2,met_cas_6311++<a href="http://g.wf" target="_blank">g.wf</a>,new;<br> punch,met_cas_6311++g.pun<br> <br>gprint,basis,orbitals=6,civector<br><br>basis=6-311++G<br>geomtype={zmat}<br>geometry={Angstrom;<br> c;<br> o,c,oc;<br> h1,c,h1c,o,h1co;<br> h2,c,h1c,o,h1co,h1,120.0;<br> h3,c,h1c,o,h1co,h1,240.0}<br> oc=1.410000, h1c=1.100000, h1co=109.100000<br><br> {uhf !uhf input with symmetry<br> occ,7,2<br> open,7.1<br> wf,17,1,1}<br> put,molden,met_uhf_6311++g.molden<br><br> {optg,space=zmat}<br> put,molden,met_opt_6311++g.molden<br> <br> {casscf;<br> occ,7,2;<br> closed,3,0;<br> wf,17,1,1;<br> state,1;<br> weight,0.5<br> wf,17,2,1;<br> state,1;<br> weight,0.5<br> start,orbital=2200.2<br>!put,molden,met_cas_6311++g_gs.molden<br> <br> CPMCSCF,GRAD,1.1,spin=0.5,accu=1.0d-7,record=5101.1<br> CPMCSCF,GRAD,1.2,spin=0.5,accu=1.0d-7,record=5102.1}<br> put,molden,met_cas_6311++g.molden<br><br> {Force<br> SAMC,5101.1<br> CONICAL,6100.1}<br><br> {Force<br> SAMC,5102.1<br> CONICAL,6100.1}<br><br> {optg,startcmd=casscf}<br> put,molden,met_cas_6311++g_con.molden<br> {frequencies}<br><br clear="all"><br>-- <br>Jayashree<br> </div></div></div> _______________________________________________<br> Molpro-user mailing list<br><a href="mailto:Molpro-user@molpro.net" target="_blank">Molpro-user@molpro.net</a><br><a href="http://www.molpro.net/mailman/listinfo/molpro-user" target="_blank">http://www.molpro.net/mailman/listinfo/molpro-user</a><br> </blockquote></div><br></div></div></blockquote></div><br><br clear="all"><br>-- <br>Jayashree<br> </div></blockquote></div><br></div></body></html>