[molpro-user] SACASSCF in MOLPRO & ORCA
Grant Hill
grant.hill at sheffield.ac.uk
Wed Jan 14 16:36:32 GMT 2015
Dear Davood,
Have you tried rotating the orbitals to produce the active space you desire?
See the following manual page: http://www.molpro.net/info/2012.1/doc/manual/node240.html
Best wishes,
Grant
> On 13 Jan 2015, at 09:27, Davood Alizadeh <alizadeh_davood at yahoo.com> wrote:
>
>
> Dear Molpro experts,
>
> Please accept my apologies for my long message. I try to be as concise as possible.
>
> I`m trying to calculate the excitation energies (EEs) of a diatomic molecule (FeAg) using the Molpro and ORCA quantum chemistry packages. What I`m willing to obtain is "identical" excitation energies with these two codes. Despite the slight, at least in my opinion, differences in the SA-CASSCF optimization algorithms implemented in these two codes (e.g.,
> 1) CSF-based optimization of ORCA Vs determinant-based optimization of Molpro in SA-CASSCF calculations
> 2) non-linear coupled optimization of molpro (Werner) Vs uncoupled optimizations (Newton-Rouphson, DIIS, ...) of ORCA
> .
> .
> .)
>
> I`m employing identical basis sets, active spaces, inactive (closed) spaces, etc in these two programs. Thus, I think expecting identical results (either energy deference or absolute energies) might be totally warranted.
>
> The thing is this is the case "just" for a CAS space of (9e,7o) spanned by the atomic {molecular} representations (4s3d^Fe) and (5s^Ag) {sig(3), delta, and pi}, i.e., using this active space, these two codes give identical EEs and absolute energies. However, when the full valence space of (19e,12o), consisting of (4s3d^Fe) and (5s4d^Ag) {sig(4), delta (2), and pi(2)} which is a more adequate/realistic one, is used the Molpro results show considerably different EEs from those of ORCA. I need to confess that these differences which is about 2500 cm^-1 (at the worst case) cannot be considered "huge" but closer results are required for the system at hand.
>
> I think, basically, these discrepancies between EEs of the two codes is due to the following compositions of natural MOs (in irrep A_1) optimized at the CAS(19e,12o) level of theory (from 15.1 to 20.1 is active):
> Orb Occ Energy Coefficients
> ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
>
> 1 1s 1 1s 1 1s 1 1s 1 1s 1 1s 1 1s 1 1s 1 1s 1 1s
> 1 1s 1 1s 1 1s 1 1s 1 2pz 1 2pz 1 2pz 1 2pz 1 2pz 1 2pz
> 1 2pz 1 2pz 1 2pz 1 2pz 1 3d0 1 3d2+ 1 3d0 1 3d2+ 1 3d0 1 3d2+
> 1 3d0 1 3d2+ 1 3d0 1 3d2+ 1 4f0 1 4f2+ 1 4f0 1 4f2+ 1 4f0 1 4f2+
> 1 5g0 1 5g4+ 1 5g2+ 2 1s 2 1s 2 1s 2 1s 2 1s 2 1s 2 1s
> 2 1s 2 1s 2 1s 2 1s 2 1s 2 2pz 2 2pz 2 2pz 2 2pz 2 2pz
> 2 2pz 2 2pz 2 2pz 2 2pz 2 3d0 2 3d2+ 2 3d0 2 3d2+ 2 3d0 2 3d2+
> 2 3d0 2 3d2+ 2 3d0 2 3d2+
> 14.1 2.00000 -0.502146 -0.001015 -0.000011 -0.000088 -0.000423 -0.001134 0.000337 0.004706 0.006334 -0.002624 -0.014412
> -0.011738 0.002893 0.090524 -0.033874 0.003529 0.000112 0.000271 -0.002368 -0.007818 -0.001503
> -0.007113 0.037722 0.036990 -0.018287 0.007173 0.000000 0.006388 0.000000 0.000198 0.000000
> 0.024728 0.000000 -0.004631 0.000000 0.000080 0.000000 0.000223 0.000000 0.002026 0.000000
> 0.000075 0.000000 0.000000 -0.000033 -0.000004 -0.000017 0.000296 0.000680 -0.000543 -0.001423
> 0.001182 -0.001467 0.004694 -0.002035 -0.035825 0.000509 0.000045 -0.000310 -0.002299 0.003527
> -0.005320 0.011943 -0.011928 0.043778 -0.253219 0.000000 0.010008 0.000000 0.370894 0.000000
> 0.493947 0.000000 0.310074 0.000000
>
> 15.1 2.00000 -0.498811 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
> 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
> 0.000000 0.000000 0.000000 0.000000 0.000000 0.000815 0.000000 -0.000031 0.000000 0.001877
> 0.000000 -0.003179 0.000000 0.013680 0.000000 0.000047 0.000000 -0.000177 0.000000 0.001064
> 0.000000 0.000000 0.000021 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
> 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000
> 0.000000 0.000000 0.000000 0.000000 0.000000 -0.254068 0.000000 0.010335 0.000000 0.375990
> 0.000000 0.494604 0.000000 0.320878
>
> 16.1 1.99873 -2.707087 -0.000010 0.000000 -0.000001 -0.000009 -0.000011 -0.000013 0.000187 0.000148 0.000024 -0.001313
> 0.000525 -0.000108 0.001382 0.000143 0.325725 0.004979 0.020291 -0.245961 -0.476994 -0.390804
> -0.094062 0.000806 -0.001811 0.000502 0.000440 0.000000 0.000508 0.000000 -0.000169 0.000000
> 0.000107 0.000000 0.000089 0.000000 0.000020 0.000000 0.000058 0.000000 -0.000115 0.000000
> -0.000008 0.000000 0.000000 -0.000048 -0.000007 -0.000019 0.000164 0.000127 0.000039 -0.000312
> -0.000632 0.000584 0.000997 -0.000840 -0.001190 -0.000553 -0.000036 0.000598 0.001010 0.000225
> -0.001080 -0.002101 -0.000195 0.000712 -0.001950 0.000000 0.000078 0.000000 0.002893 0.000000
> 0.003809 0.000000 0.002121 0.000000
> ...
> +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
> These compositions show that the optimized reference space is spanned by 15.1 (4d^Ag), 16.1 (2p^Fe) ... and the 14.1(4d^Ag) is turned out to be a core orbital whereas it is expected to have this orbital in the active space! The same happens for B_1 and B_2 irreps.
>
> This is my input by the way:
>
>
>
> +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
> SET,DKROLL=1
>
> {rhf
> wf,73,4,5;
> occ,20,8,8,3;
> closed,17,7,7,2
> orbital,2100.2
> }
>
> {casscf;occ,20,8,8,3;closed,16,7,7,2
> { ITERATIONS;
> DO,internal,2,TO,20;
> }
> start,2100.2;
> WF,73,1,3;state,3
> WF,73,2,3;state,3
> WF,73,3,3;state,3
> WF,73,4,3;state,3
> WF,73,1,5;state,3
> WF,73,2,5;state,3
> WF,73,3,5;state,3
> WF,73,4,5;state,3
> expec2,lxx,lyy,lzz;
> natorb,ci,print;
> ORBITAL,2140.2;
> }
>
> {casscf;occ,20,8,8,3;closed,14,6,6,1
> { ITERATIONS;
> DO,internal,2,TO,20;
> }
> start,2140.2;
> WF,73,1,3;state,3
> WF,73,2,3;state,3
> WF,73,3,3;state,3
> WF,73,4,3;state,3
> WF,73,1,5;state,3
> WF,73,2,5;state,3
> WF,73,3,5;state,3
> WF,73,4,5;state,3
> expec2,lxx,lyy,lzz;
> natorb,ci,print;
> ORBITAL,2140.2;
> }
> +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++
>
>
> Could someone help me about this problem please?
>
>
>
>
> Thanks a lot in advance,
> sincerely yours.
> Davood.
>
>
>
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