Dear Molpro Users!<div><br></div><div>I'm trying to do some calculations of Spin - Orbit coupling for KLi diatomic molecule </div><div>I'm using ECP approach in my calculations rather than Breit-Pauli operator.</div>
<div><br></div><div>Here's my input file:</div><div><br></div><div><div>***,kli</div><div><br></div><div>memory,100,m;</div><div><br></div><div>GPRINT,BASIS,DISTANCE,ANGLES,ORBITAL,CIVECTOR,PAIRS,CP,CS,REF,PSPACE,MICRO,VARIABLE,OPTIONS,THRESHOL,ZMATRIX,MPPERR,OPERATOR,EXTENSIO;</div>
<div>rvec=[30.] </div><div>!rvec=[70,40.,20.,10.,3.]</div><div><br></div><div>do i=1,#rvec</div><div>rkli=rvec(i)</div><div><br></div><div>geometry={li;k,li,rkli}</div><div><br></div><div>basis={</div><div><br></div><div>
ecp,li,ecp2sdf;</div><div><br></div><div>ECP,k,18,3,3;</div><div>1; 2,1.000000,0.000000; </div><div>1; 2,0.853000,13.564000; </div><div>1; 2,0.369600,2.648000; </div><div>1; 2,0.663900,-4.517000;</div><div><br></div><div>
1; 2,0.853000,-0.4; </div><div>1; 2,0.369600,1.0; </div><div>1; 2,0.663900,1.0;</div><div><br></div><div><br></div><div>s,li,ecp2sdf;</div><div>s,li,15.385230,0.010159;</div><div><br></div><div>p,li,ecp2sdf;</div><div>p,li,4.076012,0.007058;</div>
<div><br></div><div>d,li,cc-pV5Z;</div><div>d,li,1.043103,0.026579;</div><div><br></div><div>f,li,cc-pV5Z;</div><div>f,li,0.556818,0.055000;</div><div><br></div><div>s,k,ecp18sdf;c;</div><div>s,k,4.535573,0.009433;</div><div>
<br></div><div>p,k,ecp18sdf;c;</div><div>p,k,0.940156,0.004358;</div><div><br></div><div>d,k,ecp10mdf;c;</div><div>d,k,3.954897,0.010789;</div><div><br></div><div>f,k,ecp10mdf;c;</div><div>f,k,1.680236,0.029604;</div><div>
<br></div><div>}</div><div> </div><div>{cpp,init,1;</div><div>li,1,0.1915,,,0.831;}</div><div><br></div><div>{cpp,init,1;</div><div>k,1,5.354,,,0.29;}</div><div><br></div><div><br></div><div>{rhf;occ,1,0,0,0;wf,2,1,0;}</div>
<div><br></div><div><br></div><div>{multi,maxit=50;occ,3,2,2,0;</div><div>wf,2,1,2;state,3;</div><div>wf,2,2,2;state,2;</div><div>wf,2,3,2;state,2;}</div><div><br></div><div><br></div><div>{ci,nocheck;occ,3,2,2;option,maxit=199,maxiti=500;wf,2,1,0;save, 3010.1;state,3;}</div>
<div>{ci,nocheck;occ,3,2,2;option,maxit=199,maxiti=500;wf,2,1,2;save, 3012.1;state,3;}</div><div><br></div><div>lsint;</div><div><br></div><div>{ci;hlsmat,ecp,3010.1,3012.1;}</div><div><br></div><div><br></div><div><br></div>
<div>I get some errors: </div><div><br></div><div>1) First is (this error occures even if I do simple RHF procedure for molecules that contains Li ) </div><div>When I was making my calculations in 2006.1 version of molpro (without SO coupling, just simple rhf, multi and ci) I didn't get this error.</div>
<div>Why Li is treated as a unimplemented atom ?</div><div><br></div><div><div>1PROGRAM * RHF-SCF (CLOSED SHELL) Authors: W. Meyer, H.-J. Werner</div><div><br></div><div><br></div><div> NUMBER OF ELECTRONS: 1+ 1- SPACE SYMMETRY=1 SPIN SYMMETRY=Singlet </div>
<div> CONVERGENCE THRESHOLDS: 1.00E-05 (Density) 1.00E-07 (Energy)</div><div> MAX. NUMBER OF ITERATIONS: 60</div><div> INTERPOLATION TYPE: DIIS</div><div> INTERPOLATION STEPS: 2 (START) 1 (STEP)</div>
<div> LEVEL SHIFTS: 0.00 (CLOSED) 0.00 (OPEN) </div><div><br></div><div> Number of closed-shell orbitals: 1 ( 1 0 0 0 )</div><div><br></div><div><br></div><div><br></div><div> Unimplemented atom: LI No density guess!</div>
<div><br></div></div><div><br></div><div>2) Second is in CI procedure :</div><div><br></div><div><div>Coefficients of doubly external configurations greater than 0.0500000</div><div> =====================================================================</div>
<div><br></div><div> PAIR I J -> K L NP SYM REF COEFFICIENTS</div><div><br></div><div> 1 2.3 2.3 4.2 4.2 1 1 3 0.00000354 -0.00024202 -0.15885604</div><div> 1 2.3 2.3 4.3 4.3 1 1 3 0.00000354 -0.00024205 -0.15884053</div>
<div> 1 2.3 2.3 4.2 10.2 1 1 3 0.00000583 0.00006029 0.09289244</div><div> 1 2.3 2.3 4.3 10.3 1 1 3 0.00000583 0.00006029 0.09289243</div><div> 1 2.3 2.3 10.2 10.2 1 1 3 -0.00000410 0.00006513 -0.05687544</div>
<div> 1 2.3 2.3 10.3 10.3 1 1 3 -0.00000410 0.00006514 -0.05687519</div><div> </div><div> ? Error</div><div> ? Insufficient overlap</div><div> ? The problem occurs in cihdia</div></div><div><br></div>
<div><br></div><div>I tried to increase NSTATI but without any results, if I increase NSTATI too much i get </div><div>"MORE STATES THAN CONFIGURATIONS SPECIFIED"</div><div><br></div><div><br></div><div>Can you have any ideas ?</div>
<div><br></div><div>Do you have any practice in calculating SO Coupling but with using ECP approach rather than Breit-Pauli operator?</div><div><br></div><div><br></div><div>Thank you very much,</div><div><br></div><div>£ukasz Mi±dowicz</div>
<div><br></div><br>-- <br><span style="font-family:arial, sans-serif;font-size:13px;border-collapse:collapse">Department of Theoretical Physics and Quantum Informatics<br>Faculty of Applied Physics and Mathematics<br>Gdansk University of Technology<br>
ul. Gabriela Narutowicza 11/12<br>80-233 Gdansk, Poland</span><br>
</div>