molpro2002.6 ECP bug?
Nick Wilson
N.Wilson at bham.ac.uk
Mon Aug 18 23:04:02 BST 2003
Dear Jacek and Kirk,
It looks as if this discrepancy first appears in patch numfreq3 in version
2002.4 and so is probably related to bug 550
http://www.molpro.net/bugzilla/show_bug.cgi?id=550
I'll let you know when there's a fix.
Best wishes,
Nick Wilson
On Monday 18 August 2003 9:10 pm, Kirk Peterson wrote:
> Jacek,
>
> After I sent this earlier email, I happened to be in the process of
> running some
> calculations on XeF4, also using an ECP (although small-core). If I
> included tight f
> functions in the basis set (for a core-valence calculation), the RHF
> program completely
> failed even when given the correct occupation. I was able to
> successfully do the calculation by
> first running a RHF without the extra tight functions and then
> following this with another
> RHF with the tight functions and the RHF then easily converged.
>
> Perhaps Nick or someone could look into this?
>
> -Kirk
>
> On Monday, August 18, 2003, at 09:30 AM, Kirk Peterson wrote:
> > Dear Jacek,
> >
> > in 2002.6 the default initial guess in the RHF program is often quite
> > poor when ECP's are
> > used. If you include explicit "occ" and "closed" commands it will of
> > course work
> > fine. I believe the molpro folks are aware of this problem and are
> > working on a
> > fix.
> >
> > -Kirk
> >
> > On Monday, August 18, 2003, at 06:51 AM, Jacek Klos wrote:
> >> Dear Molpro Users,
> >>
> >> I hit such a problem when using effective core potential for
> >> Xe atom in interaction with NO molecule. In molpro 2002.3 and
> >> molpro 2000.1 input I use works and gives RCCSD(T) energy of the
> >> Xe-NO molecule. But when the same input is used in molpro 2002.6
> >> I get different solution of RHF program and RCCSD is exiting with
> >> UNREASONABLE NORM error. The CCSD exits because of something wrong
> >> is going in RHF I presume. Here is the input:
> >>
> >> ***,Xe-NO
> >> memory,15,m
> >> gthresh,energy=1.d-9;
> >> gprint,basis;
> >> geometry={noorient;
> >> q1;
> >> q2,q1,1.0
> >> N,q1,rnx,q2,90.0;
> >> O,q1,rox,q2,90.0,N,180.0;
> >> Xe,q1,r,q2,beta,N,0.0
> >> Be,q1,rbe,q2,beta,N,0.0;
> >> }
> >> rox=0.5371799322 ang
> >> rnx=0.6135900677 ang
> >> theta=0.0
> >> beta=90.0-theta
> >> basis={
> >> ecp,Xe,ECP46MWB;
> >> spdf,Xe,ECP46MWB;
> >> spdf,n,avtz;c;
> >> spdf,o,avtz;c;
> >> sp,be,0.9,0.3,0.1;
> >> df,be,0.6,0.2;
> >> g,be,0.3;}
> >> r=20.0 ang
> >> rbe=r*0.5 ang
> >> text,calculation for complex BIS ;
> >> dummy,be
> >> rhf;wf,23,2,1;maxit,90
> >> orbprint,0
> >> rccsd(t);maxit,90;
> >> ---
> >>
> >> In Molpro 2002.3 RHF energy is:-144.56731345
> >> but in 2002.6 version RHF is:-143.91398149
> >>
> >>
> >> First iterations in RHF in 2002.3 and 2002.6 versions:
> >>
> >> RHF iterations from Molpro 2002.6:
> >>
> >>
> >> ITERATION DDIFF GRAD ENERGY 2-EL.EN.
> >> DIPOLE MOMENTS DIIS
> >> 1 .000D+00 .000D+00 -70.56488111 444.580663
> >> .000000 301.451947 .000000 0
> >> 2 .000D+00 .221D+00 -73.15131316 170.093612
> >> .000000 ********** .000000 0
> >> 3 .628D+00 .803D-01 -87.90178385 402.689735
> >> .000000 301.531151 .000000 1
> >> 4 .364D+00 .179D+00 -73.02868137 169.716549
> >> .000000 ********** .000000 1
> >> 5 .365D+00 .934D-01 -102.53801608 355.594529
> >> .000000 301.571132 .000000 2
> >> 6 .245D+00 .125D+00 -111.74460806 317.557998
> >> .000000 302.670775 .000000 3
> >> 7 .901D-01 .884D-01 -134.11525158 234.103093
> >> .000000 189.863457 .000000 4
> >> 8 .928D-01 .400D-01 -139.43368935 146.100659
> >> .000000 ********** .000000 5
> >> 9 .692D-01 .222D-01 -142.37680048 200.240607
> >> .000000 74.352007 .000000 6
> >> 10 .516D-01 .199D-01 -142.61964648 196.806101
> >> .000000 74.632483 .000000 7
> >>
> >> RHF iterations from Molpro 2002.3:
> >>
> >> ITERATION DDIFF GRAD ENERGY 2-EL.EN.
> >> DIPOLE MOMENTS DIIS
> >> 1 .000D+00 .000D+00 -70.56488111 444.580663
> >> .000000 301.451947 .000000 0
> >> 2 .000D+00 .221D+00 -75.05389406 167.962428
> >> .000000 ********** .000000 0
> >> 3 .627D+00 .849D-01 -87.90178428 402.689735
> >> .000000 301.531150 .000000 1
> >> 4 .364D+00 .179D+00 -77.68623161 161.516536
> >> .000000 ********** .000000 1
> >> 5 .581D+00 .924D-01 -102.27524477 356.553891
> >> .000000 301.551912 .000000 2
> >> 6 .515D+00 .126D+00 -112.19090149 317.041387
> >> .000000 303.057258 .000000 3
> >> 7 .110D+00 .866D-01 -139.77210755 219.054895
> >> .000000 112.749107 .000000 4
> >> 8 .104D+00 .322D-01 -144.47518819 169.737969
> >> .000000 .217617 .000000 5
> >> 9 .452D-01 .816D-02 -144.52805483 170.443554
> >> .000000 -.231275 .000000 6
> >> 10 .803D-02 .508D-02 -144.54885496 171.414992
> >> .000000 .079383 .000000 7
> >>
> >> First iteration is the same, third very similar, but then it starts to
> >> deviate and final solution is different.
> >> I checked in case of Kr, which interest me more, there is no problem
> >> when I choose aug-cc-pv*z basis, but when I choose ECP potential for
> >> Kr
> >> the Molpro 2002.6 exits with similar error like in case of Xe atom.
> >>
> >> I checked if it can be the reason of bond-functions. No, this behavior
> >> repeats without bond functions as well. I checked if it happens only
> >> for
> >> Xe atom. No, Xe atom alone finishes in the same way in both revisions
> >> of
> >> Molpro using ECP potential.
> >>
> >> Why the same input for Xe-NO dimer behaves differently in these 2
> >> revisions of Molpro 2002?
> >>
> >> Platform used: IBM AIX 5.1
> >>
> >> Anybody with similar problem before?
> >>
> >> Best regards
> >> --
> >> Jacek A. Klos
> >> ---------------------------------
> >> Quantum Chemistry Laboratory |
> >> Department of Chemistry |
> >> University of Warsaw |
> >> Pasteura 1 Street |
> >> 02-093 Warsaw |
> >> Poland |
> >> (+4822)8220211 ext. 213 |
> >> e-mail: jakl at tiger.chem.uw.edu.pl|
> >> ---------------------------------
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