[molpro-user] water monomer excitation energy

[Peterson, Kirk]

Dear Martin,

by default, Molpro puts this molecule in the xy plane.  If you turn on orbital printing, you’ll notice that it is symmetry 3 that contains the out-of-plane pz basis functions, not symmetry 2.  Spectroscopists will refer to that former symmetry at B1 even though Molpro happens to label it as B2.  Changing your input to symmetry 3 gives you an excitation energy around 7.6 eV.

It’s good to try to reproduce other people’s work as long as you don’t propagate their mistakes as well…..

best,

-Kirk


On Dec 21, 2014, at 1:16 PM, Martin Spenke <martinspenke at yahoo.de<mailto:martinspenke at yahoo.de>> wrote:

Dear Kirk,

Unfortunately i need the first excitation energy with B1 symmetry which is 7.5 eV.
Other state energies with different irreps are well reproduced but the B1 !
"One has to note which corresponds to out-of-plane symmetry in order to match convention"
How can i do this in the input file ? Is there any specific keyword for that ?

Aug-cc basis set is used here to be able to compare the results with those of Chipman results  J. Chem. Phys. 132, 244307 (2010)

Bests
Martin


"Peterson, Kirk" <kipeters at wsu.edu<mailto:kipeters at wsu.edu>> schrieb am 20:48 Sonntag, 21.Dezember 2014:


Dear Martin,

try sym=3 rather than sym=2 (B1 and B2 labels can be a bit tricky. One has to note which corresponds to out-of-plane symmetry in order to match convention)

Also, somewhat unrelated, but it is not good practice at all to correlate all the electrons with just a valence basis set as you do here.

best,

-Kirk


On Dec 20, 2014, at 4:09 AM, Martin Spenke <martinspenke at yahoo.de<mailto:martinspenke at yahoo.de>> wrote:

Dear all,

I try to calculate the first excitation energy of water monomer which is nearly 7.5 eV by mrci method,
but from what ever reason i get a very wrong result. I also tested different active spaces but no chance !

memory,80,m
gthresh,energy=1.d-08

angstrom
geomtyp=xyz
geometry={
O   0.000 0.000 0.0
H   0.757 0.586 0.0
H  -0.757 0.586 0.0
}
basis=aug-cc-pVQZ
!---------------------------------------
{hf;wf,10,1;}
!---------------------------------------
{multi;occ,6,2,2,0;closed,0;frozen,0;wf,10,sym=2;state,1}
!---------------------------------------
{mrci;occ,6,2,2,0;closed,0;core,0;wf,10,sym=2;state,1}
!---------------------------------------

Any idea why this is the case ?

Bests
Martin

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