Dear Molpro developers,<br><br> 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.<br>
<br>My input and key output files:<br>***,<br>memory,50,m;<br>basis=3-21G;<br>gprint,civector;<br>geomtyp=xyz<br>symmetry,noSym<br>geometry={<br>2<br><br> H 0.0000000000 0.0000000000 0.0061468834<br>
H 0.0000000000 0.0000000000 0.7638536466<br>}<br>{casscf;occ,2;<br>wf,charge=0,symmetry=1,spin=0;<br>cpmcscf,hess<br>}<br>{frequencies,analytical<br>NOPROJECT<br>print,HESSIAN<br>}<br><br>----<br>
Analytical OUT (freq: 17056.95i & 3405.30):<br>
Force Constants (Second Derivatives of the Energy) in [a.u.]<br> GX1 GY1 GZ1 GX2 GY2<br> GX1 0.0000000<br> GY1 0.0000000 0.0000000<br>
GZ1 0.0000000 0.0000000 0.4272245<br> GX2 0.0000000 0.0000000 0.0000000 0.0000000<br> GY2 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000<br>
GZ2 0.0000000 0.0000000 -0.4171987 0.0000000 0.0000000<br> GZ2<br> GZ2 -11.0826665<br><br>----<br>Numerical OUT (freq. 4265.22):<br> Force Constants (Second Derivatives of the Energy) in [a.u.]<br>
GX1 GY1 GZ1 GX2 GY2<br> GX1 0.0483359<br> GY1 0.0000000 0.0029962<br> GZ1 0.0018526 0.0000000 0.0033110<br>
GX2 0.0535733 0.0000000 0.0239807 -0.1071465<br> GY2 0.0000000 -0.0123250 0.0000000 0.0000000 0.0246499<br> GZ2 -0.0276819 0.0000000 -0.0216877 0.0000038 0.0000000<br>
GX3 -0.1019092 0.0000000 -0.0258338 0.0535733 0.0000000<br> GY3 0.0000000 0.0093287 0.0000000 0.0000000 -0.0123250<br> GZ3 0.0258335 0.0000000 0.0183767 -0.0239705 0.0000000<br>
GZ2 GX3 GY3 GZ3<br> GZ2 0.0433754<br> GX3 0.0276845 0.0483359<br> GY3 0.0000000 0.0000000 0.0029962<br>
GZ3 -0.0216877 -0.0018486 0.0000000 0.0033110<br><br><br>---<br> ***,<br> memory,50,m;<br> basis=3-21G;<br> gprint,civector;<br> geomtyp=xyz<br> symmetry,noSym<br> geometry={<br> 3<br> H -0.0473124562 0.0000000000 0.0000000000<br>
H 0.9000000000 0.0000000000 0.0000000000<br> H 1.8473124562 0.0000000000 0.0000000000<br> }<br> {casscf;occ,3;<br> wf,charge=0,symmetry=1,spin=1;<br> cpmcscf,hess<br> }<br>
{frequencies,analytical<br> NOPROJECT<br> print,HESSIAN<br> }<br><br>---<br>Analytical OUT (no imag. freq., but 4283.32):<br> Force Constants (Second Derivatives of the Energy) in [a.u.]<br> GX1 GY1 GZ1 GX2 GY2<br>
GX1 0.3154326<br> GY1 0.0000000 0.0055635<br> GZ1 0.0000000 0.0000000 0.0055635<br> GX2 -0.2332771 0.0000000 0.0000000 0.4665537<br>
GY2 0.0000000 -0.0128431 0.0000000 0.0000000 0.0256862<br> GZ2 0.0000000 0.0000000 -0.0128431 0.0000000 0.0000000<br> GX3 -0.0821555 0.0000000 0.0000000 -0.2332769 0.0000000<br>
GY3 0.0000000 0.0072796 0.0000000 0.0000000 -0.0128431<br> GZ3 0.0000000 0.0000000 0.0072796 0.0000000 0.0000000<br> GZ2 GX3 GY3 GZ3<br>
GZ2 0.0256862<br> GX3 0.0000000 0.3154326<br> GY3 0.0000000 0.0000000 0.0055635<br> GZ3 -0.0128431 0.0000000 0.0000000 0.0055635<br>
<br>---<br>Numerical OUT (imag. freq. 2037.45):<br> Force Constants (Second Derivatives of the Energy) in [a.u.]<br> GX1 GY1 GZ1 GX2 GY2<br> GX1 0.0484574<br>
GY1 0.0000000 0.0055637<br> GZ1 0.0000000 0.0000000 0.0055637<br> GX2 0.0527820 0.0000000 0.0000000 -0.1055641<br> GY2 0.0000000 -0.0128437 0.0000000 0.0000000 0.0256873<br>
GZ2 0.0000000 0.0000000 -0.0128437 0.0000000 0.0000000<br> GX3 -0.1012395 0.0000000 0.0000000 0.0527820 0.0000000<br> GY3 0.0000000 0.0072800 0.0000000 0.0000000 -0.0128437<br>
GZ3 0.0000000 0.0000000 0.0072800 0.0000000 0.0000000<br> GZ2 GX3 GY3 GZ3<br> GZ2 0.0256873<br> GX3 0.0000000 0.0484574<br>
GY3 0.0000000 0.0000000 0.0055637<br> GZ3 -0.0128437 0.0000000 0.0000000 0.0055637<br><br clear="all"><div>Best Wishes,<br><br>Oscar<br><br style="color:rgb(192,192,192)">
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