[molpro-user] Odd CASSCF analytic hessian results

[chung]

Dear Molpro developers,

 My two CASSCF analytic hessian results (H2 and H3) are quite different
from their corresponding numerical hessian ones. I used Molpro2012. The
numerical hessian results are very similar to analytic hessian results by
G09.

My input and key output files:
***,
memory,50,m;
basis=3-21G;
gprint,civector;
geomtyp=xyz
symmetry,noSym
geometry={
2

 H          0.0000000000        0.0000000000        0.0061468834
 H          0.0000000000        0.0000000000        0.7638536466
}
{casscf;occ,2;
wf,charge=0,symmetry=1,spin=0;
cpmcscf,hess
}
{frequencies,analytical
NOPROJECT
print,HESSIAN
}

----
Analytical OUT (freq: 17056.95i & 3405.30):
 Force Constants (Second Derivatives of the Energy) in [a.u.]
                             GX1         GY1         GZ1
GX2         GY2
           GX1           0.0000000
           GY1           0.0000000   0.0000000
           GZ1           0.0000000   0.0000000   0.4272245
           GX2           0.0000000   0.0000000   0.0000000   0.0000000
           GY2           0.0000000   0.0000000   0.0000000   0.0000000
0.0000000
           GZ2           0.0000000   0.0000000  -0.4171987   0.0000000
0.0000000
                             GZ2
           GZ2         -11.0826665

----
Numerical OUT (freq. 4265.22):
 Force Constants (Second Derivatives of the Energy) in [a.u.]
                             GX1         GY1         GZ1
GX2         GY2
           GX1           0.0483359
           GY1           0.0000000   0.0029962
           GZ1           0.0018526   0.0000000   0.0033110
           GX2           0.0535733   0.0000000   0.0239807  -0.1071465
           GY2           0.0000000  -0.0123250   0.0000000   0.0000000
0.0246499
           GZ2          -0.0276819   0.0000000  -0.0216877   0.0000038
0.0000000
           GX3          -0.1019092   0.0000000  -0.0258338   0.0535733
0.0000000
           GY3           0.0000000   0.0093287   0.0000000   0.0000000
-0.0123250
           GZ3           0.0258335   0.0000000   0.0183767  -0.0239705
0.0000000
                             GZ2         GX3         GY3         GZ3
           GZ2           0.0433754
           GX3           0.0276845   0.0483359
           GY3           0.0000000   0.0000000   0.0029962
           GZ3          -0.0216877  -0.0018486   0.0000000   0.0033110


---
 ***,
 memory,50,m;
 basis=3-21G;
 gprint,civector;
 geomtyp=xyz
 symmetry,noSym
 geometry={
 3
  H         -0.0473124562        0.0000000000        0.0000000000
  H          0.9000000000        0.0000000000        0.0000000000
  H          1.8473124562        0.0000000000        0.0000000000
 }
 {casscf;occ,3;
 wf,charge=0,symmetry=1,spin=1;
 cpmcscf,hess
 }
 {frequencies,analytical
 NOPROJECT
 print,HESSIAN
 }

---
Analytical OUT (no imag. freq., but 4283.32):
 Force Constants (Second Derivatives of the Energy) in [a.u.]
                             GX1         GY1         GZ1
GX2         GY2
           GX1           0.3154326
           GY1           0.0000000   0.0055635
           GZ1           0.0000000   0.0000000   0.0055635
           GX2          -0.2332771   0.0000000   0.0000000   0.4665537
           GY2           0.0000000  -0.0128431   0.0000000   0.0000000
0.0256862
           GZ2           0.0000000   0.0000000  -0.0128431   0.0000000
0.0000000
           GX3          -0.0821555   0.0000000   0.0000000  -0.2332769
0.0000000
           GY3           0.0000000   0.0072796   0.0000000   0.0000000
-0.0128431
           GZ3           0.0000000   0.0000000   0.0072796   0.0000000
0.0000000
                             GZ2         GX3         GY3         GZ3
           GZ2           0.0256862
           GX3           0.0000000   0.3154326
           GY3           0.0000000   0.0000000   0.0055635
           GZ3          -0.0128431   0.0000000   0.0000000   0.0055635

---
Numerical OUT (imag. freq. 2037.45):
 Force Constants (Second Derivatives of the Energy) in [a.u.]
                             GX1         GY1         GZ1
GX2         GY2
           GX1           0.0484574
           GY1           0.0000000   0.0055637
           GZ1           0.0000000   0.0000000   0.0055637
           GX2           0.0527820   0.0000000   0.0000000  -0.1055641
           GY2           0.0000000  -0.0128437   0.0000000   0.0000000
0.0256873
           GZ2           0.0000000   0.0000000  -0.0128437   0.0000000
0.0000000
           GX3          -0.1012395   0.0000000   0.0000000   0.0527820
0.0000000
           GY3           0.0000000   0.0072800   0.0000000   0.0000000
-0.0128437
           GZ3           0.0000000   0.0000000   0.0072800   0.0000000
0.0000000
                             GZ2         GX3         GY3         GZ3
           GZ2           0.0256873
           GX3           0.0000000   0.0484574
           GY3           0.0000000   0.0000000   0.0055637
           GZ3          -0.0128437   0.0000000   0.0000000   0.0055637

Best Wishes,

Oscar
-------------- next part --------------
An HTML attachment was scrubbed...
URL: <http://www.molpro.net/pipermail/molpro-user/attachments/20130706/1dae2f69/attachment.html>