[molpro-user] energy gradients
Alexander Mitrushchenkov
sasha at theochem.uni-stuttgart.de
Thu Jul 19 14:05:07 BST 2007
Dear Jeremy,
We considered in detail the bug raised by you (1411). First, you should not
use nomodel option as it slows down the convergence considerably. Second, we
were unable to reproduce NaNs you mentioned, maybe you can give more detail
about molpro version, patch level, platform and compiler you were using.
Next, I investigated the problem of numerical gradients and found that the
default values for steps produce not accurate enough gradients leading to
slow and wrong convergence. Note that the default 'optg' converge nicely. If
you wish to use numerical gradients, you should reduce steps to say 0.001 for
distances and 0.1 for angles, and use 4-point formulae for derivatives. Then
it gives exactly the same answer as analytic gradients. Most probably, your
system is highly anharmonic. With this, I close bug 1411.
Best wishes,
Sasha
On Wednesday 09 May 2007 17:54, Jeremy Merritt wrote:
> Dear Molpro Users,
> For some reason I cant get my frequency calculation to calculate the
> forces numerically. Instead it defaults to the alaska program to
> calculate the gradients which also fails.
> Note the geometry optimization works fine using the numerical gradients,
> but the analytical gradients also fail. In the molpro manual it says
> that analytical gradients should be available for RKS so i'm not sure
> what is going wrong. I'm using version 2006.1
> Any help would be appreciated.
>
> My input is for the C6H5 radical:
> basis={
> !
> ! Literature Citation
> !Elements
> References
> !--------
> ----------
> ! H : T.H. Dunning, Jr. J. Chem. Phys. 90, 1007
> (1989).
> ! He : D.E. Woon and T.H. Dunning, Jr. J. Chem. Phys. 100, 2975
> (1994).
> !Li - Ne: T.H. Dunning, Jr. J. Chem. Phys. 90, 1007
> (1989).
> !Na - Mg: D.E. Woon and T.H. Dunning, Jr. (to be
> published)
> !Al - Ar: D.E. Woon and T.H. Dunning, Jr. J. Chem. Phys. 98, 1358
> (1993).
> !Ca : J. Koput and K.A. Peterson, J. Phys. Chem. A, 106, 9595
> (2002).
> !
> ! POLARIZATION AND/OR DIFFUSE FUNCTIONS
> !Elements
> References
> !--------
> ---------
> ! H : T.H. Dunning, Jr. J. Chem. Phys. 90, 1007
> (1989).
> ! He : D.E. Woon and T.H. Dunning, Jr., J. Chem. Phys. 100, 2975
> (1994).
> ! B - F: R.A. Kendall, T.H. Dunning, Jr. and R.J. Harrison, J. Chem.
> Phys. 96,
> ! 6769
> (1992).
> !Al - Cl: D.E. Woon and T.H. Dunning, Jr. J. Chem. Phys. 98, 1358
> (1993).
> !
> ! HYDROGEN (4s,1p) -> [2s,1p]
> ! HYDROGEN Diffuse (1s,1p)
> s,H
> ,0.130100000E+02,0.196200000E+01,0.444600000E+00,0.122000000E+00,0.29740000
>0E-01 c,1.4, 0.196850000E-01, 0.137977000E+00, 0.478148000E+00,
> 0.501240000E+00 c,4.4, 0.100000000E+01
> c,5.5, 0.100000000E+01
> p,H ,0.727000000E+00,0.141000000E+00
> c,1.1, 0.100000000E+01
> c,2.2, 0.100000000E+01
> !
> ! CARBON (9s,4p,1d) -> [3s,2p,1d]
> ! CARBON Diffuse (1s,1p,1d)
> s,C
> ,0.666500000E+04,0.100000000E+04,0.228000000E+03,0.647100000E+02,0.21060000
>0E+02,0.749500000E+01,0.279700000E+01,0.521500000E+00,0.159600000E+00,0.4690
>00000 E-01
> c,1.9, 0.692000000E-03, 0.532900000E-02, 0.270770000E-01,
> 0.101718000E+00, 0.274740000E+00, 0.448564000E+00, 0.285074000E+00,
> 0.152040000E-01,-0.319100000E-02
> c,1.9,-0.146000000E-03,-0.115400000E-02,-0.572500000E-02,-0.233120000E-01,-
>0.639550000E-01,-0.149981000E+00,-0.127262000E+00, 0.544529000E+00,
> 0.580496000E+00
> c,9.9, 0.100000000E+01
> c,10.10, 0.100000000E+01
> p,C
> ,0.943900000E+01,0.200200000E+01,0.545600000E+00,0.151700000E+00,0.40410000
>0E-01 c,1.4, 0.381090000E-01, 0.209480000E+00, 0.508557000E+00,
> 0.468842000E+00 c,4.4, 0.100000000E+01
> c,5.5, 0.100000000E+01
> d,C ,0.550000000E+00,0.151000000E+00
> c,1.1, 0.100000000E+01
> c,2.2, 0.100000000E+01
> }
>
> rCH1 = 1.09120546
> rCH2 = 1.09162863
> rCH3 = 1.09089510
> rCC1 = 1.39879138
> rCC2 = 1.40815682
> R = 2.71902477
> aHCC1 = 119.33852066
> aHCC2 = 120.33442982
> aHCC3 = 119.84978525
> aHCC4 = 121.17053159
>
> geometry={X,Y,ANGSTROM,
> C4,
> X, C4, 1.0,
> H3, C4, rCH1, X, 90.0,
> C3, C4, rCC1, H3, aHCC1, X, 180.0,
> C5, C4, rCC1, H3, aHCC1, X, 0.0,
> H2, C3, rCH2, C4, aHCC2, H3, 0.0,
> H4, C5, rCH2, C4, aHCC2, H3, 0.0,
> C2, C3, rCC2, H2, aHCC3, H3, 180.0,
> C6, C5, rCC2, H4, aHCC3, H3, 180.0,
> H1, C2, rCH3, C3, aHCC4, H3, 180.0,
> H5, C6, rCH3, C5, aHCC4, H3, 180.0,
> C1, C4, R, X, 90.0, H3, 180.0,
> }
>
> {RKS,B3LYP
> wf,41,1,1,0}
> {optg,numerical
> Hessian,nomodel}
> {Frequencies,NUMERICAL,SYMM=AUTO;}
> put,molden,C6H5.mol
>
> *selected output from the log file:
> *
> 1PROGRAM * ALASKA (Gradient of the energy) Author: R. Lindh
>
> Orbitals from record 2100.1
>
> Number of closed-shell orbitals: 20 ( 17 3 )
> Number of active orbitals: 1 ( 1 0 )
> Number of occupied orbitals: 21 ( 18 3 )
>
> Number of electrons= 41 Doublet Space symmetry=1
> Wavefunction type: OSCF
>
>
> DFT GRADIENT, EXFAC= .200
>
> RKS GRADIENT FOR STATE 1.1
>
> Atom dE/dx dE/dy dE/dz
>
> 1 .000000000 NaNQ NaNQ
> 2 .000000000 NaNQ NaNQ
> 3 .000000000 NaNQ NaNQ
> 4 .000000000 NaNQ NaNQ
> 5 .000000000 NaNQ NaNQ
> 6 .000000000 NaNQ NaNQ
> 7 .000000000 NaNQ NaNQ
> 8 .000000000 NaNQ NaNQ
> 9 .000000000 NaNQ NaNQ
> 10 .000000000 NaNQ NaNQ
> 11 .000000000 NaNQ NaNQ
>
> Starting task 7. CPU= 2201.10 sec, Elapsed= 2273.53 sec
> Incrementing variable H3Z2 by .010000 BOH to
> 4.619076 BOH
--
Dr. Alexander Mitrushchenkov
Universität Stuttgart
Institut für Theoretische Chemie
Pfaffenwaldring 55
D-70569 Stuttgart
Tel +49 (0)711 / 685-64409
Fax +49 (0)711 / 685-64442
Mail sasha at theochem.uni-stuttgart.de
More information about the Molpro-user
mailing list