In some rare cases, I run into an issue where Q-Chem could not determine the irrep of some orbitals in a symmetric system. This typically happens in the limit of stretched bonds or non-interacting dimers.
The warning I get is:
Warning : Irrep of orbital( 91) could not be determined
Any tips to get around this issue?
This is a really annoying problem! I believe it happens because of finite numeric thresholds and most often we observe it when there are degenerate orbitals, like in linear molecules or in the non-interacting fragments that you described.
Because any linear combination of degenerate orbitals is valid, the SCF procedure can mix them, unless there are special controls. I also think it happens more often with large bases with diffuse orbitals.
There are several things to try:
- Use new integral library by setting ‘use_libqints=true’, it shows a more robust behavior.
- Do a fake DFT calculation first (using the grid helps to resolve symmetry
of degenerate irreps):
X HF 1.0
X Slater 0.000001
and then read the orbitals into the second job using ‘scf_guess = read’
Sometimes playing with guess and SCF algorithms can help.
If desperate, try to use a smaller basis.