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Dear Bhargava,
<div><br>
</div>
<div>can you provide a simpler input (and maybe snippets of output) without all the ddr stuff to the list that displays the same problem? Presumably you just have a third state that is encroaching at some distances.</div>
<div><br>
</div>
<div>regards,</div>
<div><br>
</div>
<div>-Kirk</div>
<div><br>
<div>
<div>On Sep 14, 2013, at 6:42 AM, Bhargava Anusuri <<a href="mailto:bhargava.anusuri@gmail.com">bhargava.anusuri@gmail.com</a>> wrote:</div>
<br class="Apple-interchange-newline">
<blockquote type="cite">
<div dir="ltr">Dear molpro users,
<div> <span style="font-family:arial,sans-serif;font-size:16px"> </span><font face="arial, sans-serif"><span style="font-size:16px">I've been computing two-state potential energy curves of same symmetry for Li+ ion and NO system. For some
r(NO) values the the second state is not smooth with sharp inflections. I circumvented this problem in some cases by increasing n value in 'state,n;'. But in some cases it still persists. I tried incresing 'nstati' in CI but then the 3rd root is getting involved
and CI is not converging. Any help is greatly appreciated. Given below is my input:</span></font><br>
<div><font face="arial, sans-serif"><span style="font-size:16px">***,LiNO+ Diabatization and NACME calculation, noorient and x is removed, rno fixed at 2.4 as in paper</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">memory,300,m</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">gthresh,energy=0.32d-6</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">gprint,orbitals</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">rli=16.0d0</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">conv=0.52917725d0</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">rliang=rli*conv</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">rnang=1.28d0*conv</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">roang=-1.12d0*conv</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">geomtyp=xyz</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">geometry</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> 3</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">LiNO+ 15 degrees</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">Li rliang*sin(15) 0.00000000 rliang*cos(15)</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">N 0.00000000 0.00000000 rnang</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">O 0.00000000 0.00000000 roang</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">end</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">basis=cc-pVTZ</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">r=2.8d0</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">dr=[0,0.0002,-0.0002] !Small displacements for finite difference NACME calculation</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">reforb1=2140.2 !Orbital dumprecord at reference geometry</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">refci=6000.2 !MRCI record at reference geometry</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">savci=6100.2 !MRCI record at displaced geometries</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">text,compute wavefunction at reference geometry (C2v)</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">hf;wf,17,1,1;orbital,2100.2</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">multi;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">maxiter,40;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">pspace,0.05;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">wf,17,1,1;state,2; !X 1A1 and A 1A1 states,optimize two states of symmetry 1</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">natorb,reforb1 !Save reference orbitals on reforb1</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">noextra !Dont use extra symmetries</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> </span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">ci;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">option,maxit=40<span class="" style="white-space:pre">
</span> !MRCI at reference geometry</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">option,maxiti=3000;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">!option,nstati=5;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">closed,5;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">occ,10,3; </span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">wf,17,1,1;state,2; !X 1A1 and A 1A1 states</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">orbital,reforb1 !Use orbitals from previous CASSCF</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">save,refci; !Save MRCI wavefunction </span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">Text,Displaced geometries</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">do i=1,42 !Loop over different r values</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">data,truncate,savci+1 !truncate dumpfile after reference </span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">reforb=reforb1</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">do j=1,3 !Loop over small displacements for NACME</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">rli=r+dr(j) !Set current rh</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">!--------------------------------------------------------------------</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">conv=0.52917725d0</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">rliang=rli*conv</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">rnang=1.28d0*conv</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">roang=-1.12d0*conv</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">geomtyp=xyz</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">geometry</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> 3</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">LiNO+ 15 degrees</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">Li rliang*sin(15) 0.00000000 rliang*cos(15)</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">N 0.00000000 0.00000000 rnang</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">O 0.00000000 0.00000000 roang</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">end</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">!--------------------------------------------------------------------</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">multi;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">maxiter,40;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">pspace,0.7;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">wf,17,1,1;state,2; !Wavefunction definition</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">start,reforb !Starting orbitals</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">orbital,3140.2+j; !Dumprecord for orbitals</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">diab,reforb !Generate diabatic orbitals relative to reference geometry</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">noextra !Dont use extra symmetries</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">reforb=3141.2 !Use orbitals for j=1 as reference for j=2,3</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> </span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">ci;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">option,maxit=40</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">option,maxiti=6000;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">!option,nstati=5;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">closed,5;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">occ,10,3;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">wf,17,1,1;state,2;</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">orbital,diabatic !Use diabatic orbitals</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">save,savci+j; !Save MRCI for displaced geometries</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">eadia=energy !Save adiabatic energies for use in ddr</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">if(j.eq.1) then</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">e1(i)=energy(1) !Save adiabatic energies for table printing</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">e2(i)=energy(2)</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">end if</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">ci;trans,savci+j,savci+j; !Compute transition densities at R2+DR(j)</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">dm,7000.2+j; !Save transition densities on this record</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">ci;trans,savci+j,refci; !Compute transition densities between R2+DR(j) and R1</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">dm,7100.2+j; !Save transition densities on this record</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">ci;trans,savci+j,savci+1; !Compute transition densities between R and R2+DR(j)</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">dm,7200.2+j; !Save transition densities on this record</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">ddr</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">density,7000.2+j,7100.2+j !Densities for <R2+DR||R2+DR> and <R2+DR||R1></span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">orbital,3140.2+j,2140.2 !Orbitals for <R2+DR||R2+DR> and <R2+DR||R1></span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">energy,eadia(1),eadia(2) !Adiabatic energies</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">mixing,1.1,2.1 !Compute mixing angle and diabatic energies</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> </span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">if(j.eq.1) then !Store diabatic energies for R2 (DR(1)=0)</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> mixci(i)=mixangci(1) !Mixing angle obtained from ci vectors only</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> h11ci(i)=hdiaci(1) !Diabatic energies obtained from ci vectors only</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> h21ci(i)=hdiaci(2) !HDIA contains the lower triangle of the diabatic hamiltonian</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> h22ci(i)=hdiaci(3)</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> mixtot(i)=mixang(1) !Mixing angle from total overlap (including first-order correction)</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> h11(i)=hdia(1) !Diabatic energies obtained from total overlap</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> h21(i)=hdia(2)</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> h22(i)=hdia(3)</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">end if</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">mix(j)=mixang(1) !Store mixing angles for R2+DR(j)</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"> </span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">enddo !End loop over j</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">dchi(i)=(mix(3)-mix(2))/(dr(3)-dr(2))*pi/180 !Finite difference derivative of mixing angle</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">ddr</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">density,7201.2,7202.2,7203.2 !Compute NACME using 3-point formula</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">orbital,3141.2,3142.2,3143.2</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">states,2.1,1.1</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">nacmeci(i)=nacme</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">capr(i)=r</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">c=2.4</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">p(i)=c*capr(i)/capr(i)</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">if(i.lt.7) then</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">r=r+0.2d0</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">elseif(i.ge.7).and.(i.lt.19) then</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">r=r+0.1d0</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">elseif(i.ge.19).and.(i.lt.33) then</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">r=r+0.2d0</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">elseif(i.ge.33).and.(i.lt.37) then</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">r=r+0.5d0</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">else</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">r=r+1.0d0</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">endif</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">enddo</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">{table,p,capr,mixci,mixtot,dchi,nacmeci</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">Title,Mixing angles and non-adiabatic coupling matrix elements for LiNO+</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">save,2.4n.tab}</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">table,p,capr,e1,e2,h11ci,h22ci,h21ci</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">Title,Diabatic energies for LiNO+, obtained from CI-vectors</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">!format,'(f10.2,6f14.8)'</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">!sort,1</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px"><br>
</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">{table,p,capr,e1,e2,h11,h22,h21</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">title,Diabatic energies for LiNO+, obtained from CI-vectors and orbital correction</span></font></div>
<div><font face="arial, sans-serif"><span style="font-size:16px">save,2.4e.tab}</span></font></div>
</div>
<div style="font-family:arial,sans-serif;font-size:16px"><br>
</div>
<div style="font-family:arial,sans-serif;font-size:16px">Regards,<br>
</div>
<div style="font-family:arial,sans-serif;font-size:16px">Bhargava Anusuri,</div>
<div style="font-family:arial,sans-serif;font-size:16px">C/O Prof. Sanjay Kumar,</div>
<div style="font-family:arial,sans-serif;font-size:16px">Chemistry Dept.,</div>
<div style="font-family:arial,sans-serif;font-size:16px">IIT Madras.</div>
</div>
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