[molpro-user] EOM-CCSD second moments

[Tatiana Korona]

Dear Joseph,

This is not the problem of EOM, but a general issue with definitions of 
moments calculated by Molpro and Dalton, for the conventions used in 
Molpro see http://www.molpro.net/molpro-user/archive/all/msg01427.html. 
Since you see differences for the ground state, you can test on, e.g. SCF 
moments as well.

Best wishes,

Tatiana

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


`The man who makes no mistakes does not usually make anything.'
                                        Edward John Phelps (1822-1900)

On Fri, 18 May 2007, Joseph Lane wrote:

> I am having some difficulty understanding the one-electron properties 
> calculated with EOM-CCSD in molpro as compared to the CCSD linear response in 
> Dalton. I realise that the EOM-CCSD properties are calculated as expectation 
> and the linear response as energy derivatives, hence there should be small 
> numeric differences between the two.
>
> For ground state calculations, the dipole moments and quadrupole moments 
> calculated with both methods are the same, however the second moments are 
> different.
>
> Molpro:
>
> !CCSD_nonrel dipole moment      :      0.00000000     0.00000000 
> -0.64447126
>
> !CCSD(NOREL) expec  <1.1|QMXX|1.1>     2.937794363335
> !CCSD(NOREL) expec  <1.1|QMYY|1.1>    -3.662513450822
> !CCSD(NOREL) expec  <1.1|QMZZ|1.1>     0.724719087487
> !CCSD(NOREL) expec  <1.1|QMRR|1.1>   -53.392633597836
>
> !CCSD(NOREL) expec    <1.1|XX|1.1>   -15.839014957055
> !CCSD(NOREL) expec    <1.1|YY|1.1>   -20.239220166494
> !CCSD(NOREL) expec    <1.1|ZZ|1.1>   -17.314398474288
>
> Dalton:
>
> Total Molecular Dipole Moment
>                              au             Debye
>                  z     -0.64448139     -1.63810812
>
> Total Molecular quadrupole moment
>
>                   X              Y              Z
>              Column   1     Column   2     Column   3
>      1       2.93725559     0.00000000     0.00000000
>      2       0.00000000    -3.66309263     0.00000000
>      3       0.00000000     0.00000000     0.72583703
>
>
> Electronic second moment of charge
>
>                   X              Y              Z
>
>      1      15.83901789     0.00000000     0.00000000
>      2       0.00000000   107.37034240     0.00000000
>      3       0.00000000     0.00000000    32.24924174
>
>
> For excited state calculations, the dipole moments are again the same with 
> both codes but the quadrupole and second moments are completely different.
>
>
>
> Any help would be greatly appreciated.
>
>
>
>
>
>
>
> -- 
> Joseph Lane
> Department of Chemistry
> University of Otago
> P.O. Box 56
> Dunedin, New Zealand
> ph +64 3 479 5378
> email : jlane at alkali.otago.ac.nz