Molcas Forum

Shota Tsuru

Member

Registered: 2019-08-06

Posts: 2

Core excitation with RASSCF

Hello,

I am trying to calculate the excitation energies of C 1s core excitation from C2F4. C2F4 belongs to the D2h point group. The principal axis is taken along the C-C bond, and the molecule is put on zy-plane.

The two C 1s orbitals are 2ag and 2b1u. The final core-excited states I want belong to the B3u irreducible representation. I would like to put the two C 1s orbitals into RAS1, and put the following ten orbitals into RAS2:

6~7ag, 3b2g, 4b3g, 4~5b2u, 5~6b1u, 2~3b3u.

In this case, inactive orbitals exist between RAS2 and RAS1. Does anyone tell me how to make the input in this case?

Thanks in advance.
Shota

nikolay

Member

From: Stuttgart

Registered: 2016-03-21

Posts: 54

Re: Core excitation with RASSCF

There are three options that you need, alter, supsym and hexs.

Here is an example in C1 symmetry for 2p core-excited states. We change order for 2p orbitals to be above inactive by alter, freeze them by supsym and force single hole by hexs:

&rasscf
fileorb
valence.RasOrb
alter
 3
  1 3 31
  1 4 32
  1 5 33
supsym
 1
   3 3 4 5
spin
4
Symmetry
1
nactel
13 1 0
inactive
30
ras1
3
hexs
 1
  1
ras2
5
ciroot
75 75 1

I hope it is useful and with help of the manual you will be able to adapt to your particular case with D2h point group.

Shota Tsuru

Member

Registered: 2019-08-06

Posts: 2

Re: Core excitation with RASSCF

Thanks very much, nikolay!

I asked an experienced researcher a sample input for H2O O K-edge RIXS, and modified it for C2H4 (not C2F4, for simplicity) C K-edge XAS with help of your suggestion.

Here is the example. The RAS1 includes the C 1s orbitals with 4 active electrons. The RAS2 includes 4 ag, 2 b2g, 3 b3g, 3 b2u, and 2 b3u orbitals with 8 active electrons. I wish this successful example would help someone else.

Shota

&GATEWAY
EXPERT
Basis set
C.aug-cc-pVDZ
C1         0.000000000   0.0000000000   0.6745681548   Angstrom
End of basis
Basis set
H.aug-cc-pVDZ
H1         0.000000000   0.9336725725   1.2429336875   Angstrom
End of basis
Basis set
X....2s2p1d / Inline
0.0000000 2
*s-type diffuse functions
 8 4
.02462393 .01125334 .00585838 .00334597 .00204842 .00132364 .00089310 .00062431
   0.8164169629  -0.3545496531   0.2924009214  -0.2451639686   0.2010016106  -0.4153598584   3.0931116845  -4.7875728158
   0.3779494613  -0.5472992242   0.2663379048  -0.0323731284  -0.0445298273   1.4643641633  -4.7375790275  22.6219760433
   0.1482871691  -1.4508829805   1.4851170838  -1.6574814174   1.5183896808  -7.7110709550  -7.2244118411 -60.2779133694
  -1.7761418894   9.3012740480 -11.4023113315  12.4907862503 -11.8997550427  35.3110660817  36.6099922017 110.7785832087
   3.5711920802 -15.1110728765  19.8132306088 -24.8621133392  26.2215176190 -92.2193822041 -66.5183788177-144.7227974440
  -3.9060438223  15.3976130667 -17.7942673533  20.9816751326 -19.8390265038 134.8000005122  69.3520265856 128.9792080732
   2.3825846180  -9.0745015622  10.5854554359  -9.4851662485  -2.6178022039-104.0323428187 -40.9162079598 -69.9517446461
  -0.6325805612   2.3654108717  -2.7516475711   3.2088208847   6.8282174817  33.0003150588  10.5813455527  17.2393324345
*p-type diffuse functions
 8 4
.042335 .019254 .009988 .005689 .003476 .002242 .001511 .001055
   0.8967390352  -0.2821690218   0.1877800500  -0.1338597913   0.0808415137  -0.7947748017   2.1017592481  -2.4186201055
  -0.2228416135  -0.1239220867   0.1225139881  -0.0948841462   0.4440281439   0.6322349033  -3.9107405164  10.5916378353
   1.1017845221   0.0152318019  -0.2645618776   0.2780473935  -1.9103647100  -1.7448035122  -0.5990972772 -27.1836688769
  -1.6202657423   0.2302607781   0.2537835434  -0.2931121601   6.0417018250  13.6234740096  13.7801779332  49.4697315097
   1.5436671010   2.2802976789  -3.6552154680   3.4025024286 -19.5598749849 -35.2996815271 -28.4453203091 -65.2940577046
  -1.0117602096  -2.8625512825   5.7191139625  -6.0286101397  38.6260588718  46.0920649532  31.5869835070  59.8762757959
   0.4424884091   1.9708966482  -2.7125871392   0.9916831297 -38.2175943934 -31.7518781411 -19.6717969146 -33.9740178466
  -0.1007421872  -0.5610870089   0.9069038131   2.3314472987  14.7953145847   9.2396801746   5.3861422517   8.8771236753
* d-type diffuse functions
 8 2
.060540 .027446 .014204 .008077 .004927 .003175 .002137 .001491
   0.0870066598  -0.0749056712   0.0584866812  -0.0880996807   0.1625282793  -1.1361153691   1.9677244765  -0.9426598048
   0.1561652053  -0.1184458892   0.1005333771   0.0414966202   0.5545221442   0.6179973229  -4.5550011017   5.0122725127
   0.4241920610  -0.3853611718   0.2698379648  -0.9583429427  -0.3629182899  -1.0144957986   4.9207048239 -14.2622278876
   0.0686732303   0.2140373299  -0.1378644839   2.6433327896   3.1346304579   6.4235885502  -1.0443370815  27.6474729065
   1.0703363903  -1.0385922430   0.4198285458  -7.1578145538 -13.3568168892 -14.8841384990  -5.0676086594 -38.2935527374
  -1.4044020662   2.5576498033  -1.7964375200  16.2491823825  22.6225613932  18.2272291573   8.2272476616  36.7254428126
   1.0696924928  -1.2382246552  -0.0127540717 -19.0765443016 -18.4019917191 -12.2664212052  -5.9340491550 -21.8842148281
  -0.3377254591   0.5230050799   1.7453060061   8.5210952347   6.0681948977   3.6091976476   1.7803937684   6.0630531335
X         0.00000000   0.00000000   0.00000000 Angstrom
End of basis
ANGM
 0. 0. 0.
SYMMETRY
xy xz xyz
Douglas-Kroll
CHOLESKY
SDIP
End of input
*------------------------------------------------------------------------------
 &SEWARD &END
*EXPERT
End of input
*------------------------------------------------------------------------------
 &SCF &END
*KSDFT=B3LYP
PRORbitals
 2 1.d+10
OCCUPIED
3 0 0 1 0 1 2 1
End of input
*------------------------------------------------------------------------------
* &SCF &END
*End of input
*>> COPY $Project.scf.molden $Project.scf1.molden
*------------------------------------------------------------------------------
>> COPY $Project.ScfOrb      INPORB
 &RASSCF &END
LUMORB
SUPSYM
1
 1 1
0
0
0
0
0
1
 1 1
0
Symmetry
 1
Spin
 1
nActEl
12 1 0
ALTER
2
1 1 2
7 1 2
Inactive
1 0 0 0 0 0 1 0
Ras1
1 0 0 0 0 0 1 0
Ras2
4 2 0 3 0 3 0 2
Ras3
0 0 0 0 0 0 0 0
CIRO
1 1 1
End of input
>> COPY $Project.JobIph $Project.JobIph_S1
>> COPY $Project.rasscf.molden $Project.rasscfS1.molden
*&GRID_IT
*  name = $Project.rasscfS1
*  ASCII
*-------------------------------------------------------------------------------
 &CASPT2 &END
MAXITER
60
Multistate
1 1
IMAG
0.15
End of input
>> COPY $Project.JobMix $Project.JobMix_S1
*------------------------------------------------------------------------------
>> COPY $Project.ScfOrb      INPORB
 &RASSCF &END
LUMORB
SUPSYM
1
 1 1
0
0
0
0
0
1
 1 1
0
Symmetry
 6
Spin
 1
nActEl
12 1 0
ALTER
2
1 1 2
7 1 2
HEXS
1
1
Inactive
1 0 0 0 0 0 1 0
Ras1
1 0 0 0 0 0 1 0
Ras2
4 2 0 3 0 3 0 2
Ras3
0 0 0 0 0 0 0 0
CIRO
3 3 1
End of input
>> COPY $Project.JobIph $Project.JobIph_S1x
>> COPY $Project.RasOrb $Project.RasOrb_S1x
>> COPY $Project.rasscf.molden $Project.rasscfS1x.molden
*&GRID_IT
*  name = $Project.rasscfS1x
*  ASCII
*-------------------------------------------------------------------------------
 &CASPT2 &END
MAXITER
60
Multistate
3 1 2 3
IMAG
0.15
End of input
>> COPY $Project.JobMix $Project.JobMix_S1x
*-------------------------------------------------------------------------------
*------------------------------------------------------------------------------
>> COPY $Project.ScfOrb      INPORB
 &RASSCF &END
LUMORB
SUPSYM
1
 1 1
0
0
0
0
0
1
 1 1
0
Symmetry
 7
Spin
 1
nActEl
12 1 0
ALTER
2
1 1 2
7 1 2
HEXS
1
1
Inactive
1 0 0 0 0 0 1 0
Ras1
1 0 0 0 0 0 1 0
Ras2
4 2 0 3 0 3 0 2
Ras3
0 0 0 0 0 0 0 0
CIRO
5 5 1
End of input
>> COPY $Project.JobIph $Project.JobIph_S2x
>> COPY $Project.RasOrb $Project.RasOrb_S2x
>> COPY $Project.rasscf.molden $Project.rasscfS2x.molden
*&GRID_IT
*  name = $Project.rasscfS2x
*  ASCII
*-------------------------------------------------------------------------------
 &CASPT2 &END
MAXITER
60
Multistate
5 1 2 3 4 5
IMAG
0.15
End of input
>> COPY $Project.JobMix $Project.JobMix_S2x
*-------------------------------------------------------------------------------
*------------------------------------------------------------------------------
>> COPY $Project.ScfOrb      INPORB
 &RASSCF &END
LUMORB
SUPSYM
1
 1 1
0
0
0
0
0
1
 1 1
0
Symmetry
 8
Spin
 1
nActEl
12 1 0
ALTER
2
1 1 2
7 1 2
HEXS
1
1
Inactive
1 0 0 0 0 0 1 0
Ras1
1 0 0 0 0 0 1 0
Ras2
4 2 0 3 0 3 0 2
Ras3
0 0 0 0 0 0 0 0
CIRO
3 3 1
End of input
>> COPY $Project.JobIph $Project.JobIph_S3x
>> COPY $Project.RasOrb $Project.RasOrb_S3x
>> COPY $Project.rasscf.molden $Project.rasscfS3x.molden
*&GRID_IT
*  name = $Project.rasscfS3x
*  ASCII
*-------------------------------------------------------------------------------
 &CASPT2 &END
MAXITER
60
Multistate
3 1 2 3
IMAG
0.15
End of input
>> COPY $Project.JobMix $Project.JobMix_S3x
**-------------------------------------------------------------------------------
**------------------------------------------------------------------------------
>> COPY $Project.JobMix_S1   JOB001
>> COPY $Project.JobMix_S1x  JOB002
>> COPY $Project.JobMix_S2x  JOB003
>> COPY $Project.JobMix_S3x  JOB004
 &RASSI  &END
SpinOrbit
TRDI
Ejob
End of input