TURBOMOLE Modules > Define
ERROR: non-positive definite matrix in Cholesky decomposition (routine: usad)
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JakubV:
Dear Turbomole Experts,
I wanted to compute NUHFI with TM default suggested ECP and basis sets def2-QZVPP for N,H,F and I atoms.
For uranium, I downloaded basis set "HGBSP3-9" from https://www.basissetexchange.org/
(there is no basis set for uranium above triple zeta in the standard library, sadly. HGBSP3-9 is possibly overkill - much above def2-QZVPP level and used for all-electron calculations..., but I could not find def-QZVPP for ECP calculation)
Somewhere after I decided EHT initial guess it gave me an error message about negative eigenvalues in Cholesky decomposition.
What should be a possible workaround, please?
--- Quote ---0
NUMBER OF ELECTRONS IN YOUR MOLECULE IS 74
AUTOMATIC OCCUPATION NUMBER ASSIGNMENT ESTABLISHED !
FOUND CLOSED SHELL SYSTEM !
HOMO/LUMO-SEPARATION : 0.000171
ORBITAL SYMMETRY ENERGY DEFAULT
(SHELL) TYPE OCCUPATION
34 34a -0.39807 2
35 35a -0.36079 2
36 36a -0.33264 2
37 37a -0.24197 2
38 38a -0.24179 0
39 39a -0.24024 0
40 40a -0.23511 0
!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!
!!! WARNING ! HOMO/LUMO-SEPARATION LOWER THAN 0.05 AU !!!
!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!
DO YOU ACCEPT THIS OCCUPATION ? DEFAULT=y
y
ERROR: non-positive definite matrix in Cholesky decomposition (routine: usad)
of overlap matrix in project.f
MODTRACE: no modules on stack
negative root in usad, see output
ehtinp ended abnormally
ehtinp ended abnormally
program stopped.
--- End quote ---
Best regards,
JakubV
antti_karttunen:
Hi,
For uranium, the def-TZVPP basis set has ECP of 60 electrons, leaving 32 electrons in the valence space. This would mean that your valence space is in terms of orbitals:
s: 5s+6s+7s
p: 5p+6p+7p
d: 5d+6d
f: 5f
In the def-TZVPP basis set, you have 10 s functions, 9 p functions, 5 d functions, 4 f functions, and 3 g polarization functions. So I would say that at least on paper the basis set sounds more like a QZVPP basis set. Of course some higher angular momentum polarization functions could be added for example from cc-pVQZ-PP. cc-pVQZ-PP could also be an alternative basis set to consider (although as a generally contracted basis set it will be computationally more costly). It is available here in TM format: http://www.grant-hill.group.shef.ac.uk/ccrepo/
Best,
Antti
uwe:
Hello,
if you use define to prepare the input, it will most likely assign ECPs to the default basis set def-SV(P) automatically.
If you then switch to an all-electron basis set, please make sure to remove the ECPs before continuing. Not sure if this is related to the error you get, but I ran into this myself some time ago...
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