Molcas Forum
Support and discussions for Molcas and OpenMolcas users and developers
You are not logged in.
- Topics: Active | Unanswered
Announcement
Please note: The forum's URL has changed. The new URL is: https://molcasforum.univie.ac.at. Please update your bookmarks!
You can choose an avatar and change the default style by going to "Profile" → "Personality" or "Display".Pages: 1
#1 2024-11-13 16:20:42
- Alessandro
- Member
- Registered: 2024-09-24
- Posts: 8
Highly excited states NACs
Hello,
I've already asked some questions in the past but still facing problems.
I am trying to compute some inner valence excited states of a water dimer and the NACs between them. I'm interested in states dominated by single excitations from the 4th orbital (out of 10 orbitals in total).
Initially I did a RASSCF putting the 4th orbital in RAS1 and limiting to 1 hole in it. I get excited states with energies that make sense and the CI coefficients confirm that the excited states are generated by inner valence excitations.
However RASSCF doesn't allow to have numerical NACs calculations.
Hence I tried to do a CASSCF where substantially I use alter to put the orbital 3 and 4 (the two inner valence) instead of the HOMO - 1 and HOMO (orbital 9 and 10) and supsym.
I can compute this way the NACs (as they are implemented with CASSCF).
However I'm unsure of the results: the energies of the excited states don't convince me (lower then expected but the active space is not the best maybe) and the energies of the 'new' orbitals 9 and 10 (after the swap) are 0.000 which I don't think is correct.
Input example:
&gateway
coord
6
wd_1.0
O 1.3832027274 0.0005305073 -0.1113010031
H 1.7431113123 0.7547042488 0.3616213140
H 1.7415847054 -0.7598653852 0.3527901748
O -1.5136862649 -0.0010516718 0.1210592194
H -1.8809444243 0.0041975492 -0.7638747932
H -0.5598832934 0.0051329031 -0.0286024265
basis
cc-pvtz
group
c1
ricd
angm
0 0 0
&SEWARD
DoAnalytical
&SCF
****************the two 2a1 to Ras2 and the HOMO and HOMO-1 to inactive
&RASSCF
cionly
alter
2;1 3 9; 1 4 10
inactive
8
ras1
0
ras2
6
ras3
0
nactel
4 0 0
spin
1
&RASSCF
inactive
8
ras1
0
ras2
6
ras3
0
nactel
4 0 0
spin
1
supsym
1
2 9 10;0
*******************Inner-valence-excited state
&RASSCF
inactive
8
ras1
0
ras2
6
ras3
0
nactel
4 0 0
spin
1
ciroot
5 5 1
supsym
1
2 9 10;0
&ALASKA
&ALASKA
NAC
1 2Some part of the output are:
The SCF orbitals:
Title: SCF orbitals
Molecular orbitals for symmetry species 1: a
Orbital 1 2 3 4 5 6 7 8 9 10
Energy -20.5854 -20.5222 -1.3755 -1.3136 -0.7364 -0.6840 -0.6104 -0.5540 -0.5262 -0.4746
Occ. No. 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000But after alter they become:
Final state energy(ies):
------------------------
:: RASSCF root number 1 Total energy: -152.13293883
++ Molecular orbitals:
-------------------
Pseudonatural active orbitals and approximate occupation numbers
Molecular orbitals for symmetry species 1: a
Orbital 1 2 3 4 5 6 7 8 9 10
Energy -20.5856 -20.5226 -0.5264 -0.4750 -0.7363 -0.6841 -0.6105 -0.5542 0.0000 0.0000
Occ. No. 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 1.9968 1.9967This are the roots (which look like the inner valence excited states I want after the orbital switch):
************************************************************************************************************************
Wave function printout:
occupation of active orbitals, and spin coupling of open shells (u,d: Spin up or down)
************************************************************************************************************************
Note: transformation to natural orbitals
has been made, which may change the order of the CSFs.
printout of CI-coefficients larger than 0.05 for root 1
energy= -152.108396
conf/sym 111111 Coeff Weight
1 220000 -0.99889 0.99778
printout of CI-coefficients larger than 0.05 for root 2
energy= -150.956277
conf/sym 111111 Coeff Weight
2 2ud000 0.28121 0.07908
3 u2d000 -0.16727 0.02798
7 2u0d00 0.71841 0.51611
10 u20d00 -0.60713 0.36861
printout of CI-coefficients larger than 0.05 for root 3
energy= -150.930851
conf/sym 111111 Coeff Weight
2 2ud000 0.70406 0.49571
3 u2d000 0.69930 0.48902
5 ud2000 0.05265 0.00277
7 2u0d00 -0.06730 0.00453
10 u20d00 0.05326 0.00284
printout of CI-coefficients larger than 0.05 for root 4
energy= -150.882487
conf/sym 111111 Coeff Weight
8 2u00d0 0.70165 0.49231
11 u200d0 0.70892 0.50257
printout of CI-coefficients larger than 0.05 for root 5
energy= -150.881028
conf/sym 111111 Coeff Weight
2 2ud000 0.64599 0.41731
3 u2d000 -0.68915 0.47493
7 2u0d00 -0.24406 0.05957
10 u20d00 0.20064 0.04026Finally the NACs are computed:
A total of 556329. entities were prescreened and 554601. were kept.
A total of 12940678. entities were prescreened and 9426117. were kept.
*****************************************************
* *
* CI derivative coupling *
* *
*****************************************************
Irreducible representation: a
------------------------------------------------------------------------------------------
X Y Z
------------------------------------------------------------------------------------------
O1 -1.44409826674596E-03 3.09496696355287E-05 -4.71841671060413E-03
H2 -3.11266081946319E-03 5.09881723810905E-03 2.35592701311559E-03
H3 -3.12877408271272E-03 -5.12953446970504E-03 2.29753595854456E-03
O4 -1.29534527411729E-01 7.87132746379014E-04 -1.76446449025475E-01
H5 1.08864030720357E-01 -7.82231878090929E-04 1.67733179412918E-01
H6 2.83560298602995E-02 -5.13330632716962E-06 8.77822335150870E-03
------------------------------------------------------------------------------------------
******************************************************
* *
* CSF derivative coupling *
* *
******************************************************
Irreducible representation: a
------------------------------------------------------------------------------------------
X Y Z
------------------------------------------------------------------------------------------
O1 1.72323730952940E-03 1.71659455285683E-05 -2.87343753452001E-03
H2 -1.34504199309155E-03 8.17037144795842E-03 3.70284170893777E-03
H3 -1.36703125790096E-03 -8.21584278611743E-03 3.60600160200157E-03
O4 -9.01402630276672E-02 4.81731742660597E-04 -1.14483615088680E-01
H5 1.38503247389045E-01 -1.20907392589810E-03 2.39748135778239E-01
H6 -1.90211059988831E-02 -1.50091646608465E-04 -2.74281591482908E-03
------------------------------------------------------------------------------------------
Energy difference: -1.152119E+00
*******************************************************
* *
* Total derivative coupling *
* *
*******************************************************
Irreducible representation: a
------------------------------------------------------------------------------------------
X Y Z
------------------------------------------------------------------------------------------
O1 2.97666496444648E-03 -9.69730382573865E-06 1.22198597555787E-03
H2 1.35664060104618E-03 3.74477335620605E-03 1.65797804612114E-03
H3 1.34863709484684E-03 -3.76358319323905E-03 1.61181936737059E-03
O4 2.22912540396114E-02 -2.01472423649681E-04 3.86658373504555E-02
H5 4.40130109052682E-02 -5.30123544795410E-04 9.41615018457267E-02
H6 -4.36331651841923E-02 -1.45636113172964E-04 -1.03620120340884E-02
------------------------------------------------------------------------------------------
norm: 0.1219
--- Stop Module: alaska at Wed Nov 13 15:43:52 2024 /rc=_RC_ALL_IS_WELL_ ---
--- Module alaska spent 21 seconds ---
.##################.
.# Happy landing! #.
.##################.I want to ask if you have any better idea on how to do this?
Is it an error that zero energy in orbital 9 and 10, in case how to fix it?
Thank you in advance
Offline
Pages: 1