[molpro-user] problem with dipole moment from CCSD density

[Tatiana Korona]

Hi,

You probably use molpro2010 and probably your output looks like:

  Final output for nonrelaxed part
                   ^^^^^^^^^^

  Dipole moment SCF               :     -0.00402081     0.00000000     0.88170589
  Dipole moment - correlation part:      0.17910928     0.00000000    -0.20111211
  !CCSD_nonrel dipole moment      :      0.17508847     0.00000000     0.68059378
       ^^^^^^^

So it is clearly written that you calculate the NONRELAXED dipole moment, i.e. 
this part which does not depend on relaxation of the orbitals and what people 
often call the expectation CCSD dipole moment, because it is calculated as 
<Lambda|mu_z|CC>.

With this molpro version, if you want the orbital-relaxed dipole moment, too, 
you should make an all-electron calculation (i.e. core,0) and write

{hf}

core,0
{ccsd,thrden=1.0d-11,thrvar=1.0d-11;
expec,relax,dm
}

Then your output will look like:

  Final output for nonrelaxed part
                   ^^^^^^^^^^

  Dipole moment SCF               :     -0.00402068     0.00000000     0.88170485
  Dipole moment - correlation part:      0.17929918     0.00000000    -0.19825241
  !CCSD_nonrel dipole moment      :      0.17527850     0.00000000     0.68345244
(...)
  Calculate relaxation part of CCSD density matrix
            ^^^^^^^^^^

  First make the Z vector, this will take some time

  Starting Coupled-perturbed Hartree-Fock (...)

  Dipole moment expectation values:      0.17527850     0.00000000     0.68345244
  Orbital relaxation contribution:      -0.03121461     0.00000000     0.04033210
          ^^^^^^^^^^
  !CCSD dipole moments:                  0.14406389     0.00000000     0.72378454

The orbital-relaxed and frozen-core CCSD dipole moment is available in 
molpro2012, this is a new code of W. Gyorffy.

Best wishes,

Tatiana

On Thu, 9 Jul 2015, Irikura, Karl K. Dr. wrote:

> Hi,
>
> I'm trying to compute a dipole moment using the finite-field approach, for a variety of correlated methods.  This is working, but during testing I found results that appear buggy for the correlated density.  There are only two non-zero components (Cs point group).  Here are the values I get.  The molecule is (SO2)(CO), the calc is CCSD/aug-cc-pV(D+t)Z.
>
> Frozen-core
> Code #1:  mu_x = 0.3663 D, mu_z = 1.8332 D (E = -660.852312)
> Code #2:  mu_x = 0.3653 D, mu_z = 1.8334 D (E = -660.852312)
> MOLPRO: mu_x =  0.4450 D, mu_z = 1.7298 D (E = -660.852312)
> MOLPRO, finite-field:  mu_x = 0.3656(6) D, mu_z  = 1.8325(3) D
>
> Active core
> Code #1: mu_x = 0.3672 D, mu_z = 1.8395 D (E = -660.916466)
> Code #2: mu_x = 0.3662 D, mu_z = 1.8397 D  (E = -660.916466)
> MOLPRO: mu_x = 0.4455 D, mu_z = 1.7370 D  (E = -660.916466)
> MOLPRO, finite-field: mu_x = 0.3665(6) D, mu_z = 1.8388(3) D
>
> Everything is nicely consistent at the HF level.
>
> Here is my input file:
> ~~~~~~~~~~~~~~~~~~~~~~~~~~~
> ***, SO2 CO Complex
> memory,220,m
> angstrom
> geomtyp=xyz
>
> geometry={
>    5
> UCCSD(T)/AUG-CC-PV(D+D)Z  ENERGY=-660.89251446
> S         -1.2013598699        0.0000000000        0.3645914371
> O         -1.2280384976        1.2649632874       -0.3826423804
> O         -1.2280384976       -1.2649632874       -0.3826423804
> C          2.1633891600        0.0000000000        0.1896882719
> O          3.2695357051        0.0000000000       -0.1104089492
> }
>
> basis=AUG-CC-PV(D+d)Z
> hf
> {ccsd,thrden=1.0d-11,thrvar=1.0d-11;
> expec,dm
> }
>
> show,dm*
>
> deb(1)=dmx*TODEBYE
> deb(2)=dmy*TODEBYE
> deb(3)=dmz*TODEBYE
> show,deb
>
> ~~~~~~~~~~~~~~~~~~~~~~~~~~~
>
> Please let me know if I am doing something wrong here.
>
> Thanks,
> Karl
>
>
> -------------------------------------------------------------------
> Dr. Karl K. Irikura
> National Institute of Standards and Technology
> 100 Bureau Drive, mail stop 8320
> Gaithersburg, MD 20899-8320
> voice:  301-975-2510   fax:  301-975-3670
> email:  karl.irikura at nist.gov<mailto:karl.irikura at nist.gov>
> http://www.nist.gov/mml/csd/informatics_research/index.cfm
> -------------------------------------------------------------------
>
>

Dr. Tatiana Korona http://tiger.chem.uw.edu.pl/staff/tania/index.html
Quantum Chemistry Laboratory, University of Warsaw, Pasteura 1, PL-02-093 Warsaw, POLAND