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 2022-09-14 10:36:50
- cymantren
- Member
- Registered: 2017-09-18
- Posts: 37
Ti-atom, d2-case
Hello Users and developers,
I want to calculate the different states of the Ti- d2-configuration, however the calculation seems not to be correct.
First of all using the symmetry-D2h- the scf-calc. was correct, but the CAS(6,8) was not. The RASF-energy is much lesser than that of the scf !
------------------------------
>>> COPY -FORCE OM_Ti-tripl_sym.UhfOrb INPORB
&GATEWAY
Coord
1
Coordinates in Angstrom units
Ti 0.00 0.00 0.00
Basis=Ti.ano-s.Pierloot.17s12p9d4f.8s7p7d4f..,
Title=Ti Triplet in D2h
Group=Full
End of input
&SEWARD
Title=Seward data By Gabedit
End of input
&SCF
Title=SCF data By Gabedit
UHF
ZSpin=2
End of input
&RASSCF
Title = Ti 3B1g-Zustand: CAS(6,8)
LUMORB
SPIN = 3
NACTEL = 6,0,0 *RAS2,RAS3,RAS1
INACT = 3 2 2 0 1 0 0 0 *8 MOs=16e
RAS2 = 2 0 0 2 0 2 2 0 *8 MOs
CIROOT = 2,2,1
RLXROOT = 1
End of input---> D2h
Total SCF energy -848.3999268807
CAS(6,8):
Wave function specifications:
-----------------------------
Number of closed shell electrons 16
Number of electrons in active shells 6
Max number of holes in RAS1 space 0
Max nr of electrons in RAS3 space 0
Number of inactive orbitals 8
Number of active orbitals 8
Number of secondary orbitals 76
Spin quantum number 1.0
State symmetry 1--
-->
Final state energy(ies):
------------------------
:: RASSCF root number 1 Total energy: -845.62261023
:: RASSCF root number 2 Total energy: -845.61326499-------------------------------
Then I tried using "no sym" = C1, the calculation seems to be correct,but the RAS -energy of the active space was always " 0.0" ??
However the calculations seems to be incorrect and the MOs are not in the proper order, BUT the C1 -calculation gave reasonable results.
C!-sym.
-----------------------------------
--->
Total SCF energy: -848.4113969208
Title: Natural orbitals
Molecular orbitals for symmetry species 1: a
Orbital 1 2 3 4 5 6 7 8 9 10
Energy -183.2710 -19.3458 -17.7620 -4.9478 -17.7620 -17.7620 -1.8221 -1.8221 -1.8221 -0.2208
Occ. No. 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 1.9996 1.9996 1.9996 1.9972
Orbital 11 12 13 14 15 16 17 18 19 20
Energy -0.0898 -0.0898 0.1711 2.6340 2.6340 2.6340 5.4199 5.4200 5.4201 6.8339
Occ. No. 1.0000 1.0000 0.0028 0.0004 0.0004 0.0004 0.0000 0.0000 0.0000 0.0000--> RAS(6,8)
Wave function specifications:
-----------------------------
Number of closed shell electrons 16
Number of electrons in active shells 6
Max number of holes in RAS1 space 0
Max nr of electrons in RAS3 space 0
Number of inactive orbitals 8
Number of active orbitals 8
Number of secondary orbitals 76
Spin quantum number 1.0
State symmetry 1
--
++ Orbital specifications:
-----------------------
Symmetry species 1
a
Frozen orbitals 0
Inactive orbitals 8
Active orbitals 8
RAS1 orbitals 0
RAS2 orbitals 8
RAS3 orbitals 0
Secondary orbitals 76
Deleted orbitals 0
Number of basis functions 92
--
++ CI expansion specifications:
----------------------------
Number of CSFs 1512
Number of determinants 1960
Number of root(s) required 2
Root chosen for geometry opt. 1
CI roots used 1 2
weights 0.500 0.500
highest root included in the CI 2
max. size of the explicit Hamiltonian 200
Final optimization conditions:
------------------------------
Average CI energy -848.39357908
RASSCF energy for state 1 -848.43147864
Super-CI energy -0.00000000
RASSCF energy change 0.00000000
Max change in MO coefficients -0.421E-03
Max non-diagonal density matrix element 0.503E-03
Maximum BLB matrix element -0.997E-05
(orbital pair 4, 20 in symmetry 1)
Norm of electronic gradient 0.846E-01
--
Final state energy(ies):
------------------------
:: RASSCF root number 1 Total energy: -848.43147864
:: RASSCF root number 2 Total energy: -848.35567953---> MOs
Orbital 1 2 3 4 5 6 7 8 9 10
Energy -183.2162 -21.3583 -17.7305 -17.7287 -17.7262 -2.6771 -1.7411 -1.7366 0.0000 0.0000
Occ. No. 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 2.0000 1.9952 1.4806
Orbital 11 12 13 14 15 16 17 18 19 20
Energy 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0352 0.1131 0.1158 0.1163
Occ. No. 1.4466 0.9923 0.0308 0.0046 0.0405 0.0094 0.0000 0.0000 0.0000 0.0000-----------------------------------
There are 2 Triplets (F,P) and 3 Singlets (S,D,G) which emerge from this configuration. The triplet-F state is the groundstate.
Please give me some tips, how I can overcome the problems, and/or where are input-mistakes.
Thank you in advance !
Best regards
Alfred
Offline
#2 2022-09-15 08:10:20
- Ignacio
- Administrator
- From: Uppsala
- Registered: 2015-11-03
- Posts: 1,085
Re: Ti-atom, d2-case
The higher RASSCF energy in D2h could indicate that your choice of inactive and active orbitals is not correct. Double check the identity of the orbitals (in each irrep) before and after the RASSCF calculation. Try first to quasi-reproduce the SCF calculation with a 2-in-2 active space...
Regarding the C1 calculation, the energies of the active (natural) orbitals are undefined, and displayed as zero. If you want defined energies you could compute canonical orbitals, but then the occupations would be undefined. The order of the active orbitals is irrelevant.
Offline
Pages: 1