ROHF RPA TDDFT Excited Energies Calculation of Sc Failed on Mac using PBE0 and aug-cc-pvdz


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Forum Vet
There is something happening about this calculation with NWCHEM6.8 on macOS High Sierra with GCC 7.2.0, mpich 3.2.1 and Xcode 9.2.
First, the calculation using aug-cc-pvtz could not converge
...
Entering Davidson iterations
 Unrestricted

 Iter   NTrls   NConv    DeltaV     DeltaE      Time   
---- ------ ------ --------- --------- ---------
1 10 0 0.15E+00 0.10+100 328.3
------------------------------------------------------------------------
tddft_diagon: negative excitation energy 0
------------------------------------------------------------------------.
Second, the one with aug-cc-pvdz was successful for one time
...


 Root   1         a              0.000479490 a.u.                0.0130 eV 
<S2> = 0.9633
----------------------------------------------------------------------------,
...
----------------------------------------------------------------------------
Root 2 a 0.000721485 a.u. 0.0196 eV
<S2> = 0.9615
----------------------------------------------------------------------------
...
----------------------------------------------------------------------------
Root 3 a 0.001720248 a.u. 0.0468 eV
<S2> = 0.8747
----------------------------------------------------------------------------
...


 Root   4         a              0.010212053 a.u.                0.2779 eV 
<S2> = 0.7555
----------------------------------------------------------------------------
...
but failed when the computer was restarted using the same input
...Entering Davidson iterations
 Unrestricted

 Iter   NTrls   NConv    DeltaV     DeltaE      Time   
---- ------ ------ --------- --------- ---------
1 10 0 0.15E+00 0.10+100 151.3
2 30 0 0.79E-01 0.35E-01 205.2
------------------------------------------------------------------------
tddft_diagon: negative excitation energy 0
------------------------------------------------------------------------
------------------------------------------------------------------------
current input line :
29: task tddft energy
------------------------------------------------------------------------
...

Finally, the repeated CIS TDDFT calculations had a small difference with aug-cc-pvdz:
1. ...


 Root   1         a              0.008091830 a.u.                0.2202 eV 
<S2> = 0.9172
----------------------------------------------------------------------------
...
----------------------------------------------------------------------------
Root 2 a 0.008125684 a.u. 0.2211 eV
<S2> = 0.9172
----------------------------------------------------------------------------
...
2. ...


 Root   1         a              0.008077333 a.u.                0.2198 eV 
<S2> = 0.9181
----------------------------------------------------------------------------
...


 Root   2         a              0.008115493 a.u.                0.2208 eV 
<S2> = 0.9181
----------------------------------------------------------------------------
...

GAMESS gave 0.048eV, 0.048eV and 0.284eV,which could be reproduced from different versions.

Do these mean the rohf calculation using NWCHEM was very unstable in this case and a patch is required?

Thanks a lot.

Very Best regards!