Confusion on the sign of CI coefficient in singlet state CI wavefunction in PySCF
Hello everyone,
I am facing an issue regarding the sign of CI coefficients of a CASSCF wavefunction computed by PySCF. I was running an SA-CASSCF calculation on O2 molecule with an active space of 4 orbitals and 2 electrons taking 1 triplet and 4 quartets for state-averaging. I got the following configuration for each state in the output,
** Largest CI components **** Largest CI components **
[alpha occ-orbitals] [beta occ-orbitals] state 0 CI coefficient
[0 1] [] -0.999961442607
[alpha occ-orbitals] [beta occ-orbitals] state 1 CI coefficient
[0] [0] -0.670677953622
[1] [1] 0.737204894786
[alpha occ-orbitals] [beta occ-orbitals] state 2 CI coefficient
[0] [1] 0.704828210369
[1] [0] 0.704828187689
[alpha occ-orbitals] [beta occ-orbitals] state 3 CI coefficient
[0] [0] 0.738528199450
[1] [1] 0.671826029081
[alpha occ-orbitals] [beta occ-orbitals] state 4 CI coefficient
[1] [2] -0.705973331057
[2] [1] -0.705973124345
The corresponding S^2 values are,
state 0 E = -149.65917380939 S^2 = 2.0000000
state 1 E = -149.612964346535 S^2 = 0.0000000
state 2 E = -149.612300584601 S^2 = 0.0000000
state 3 E = -149.568898604759 S^2 = 0.0000000
state 4 E = -149.177928151749 S^2 = 0.0000000
Looking at the alpha and beta occupations, state 2 appears to be an open-shell singlet state which is an approximate linear combination of |αβ00⟩ and |βα00⟩. To the best of my understanding the open-shell singlet state can be represented as 1/(√2)(|αβ00⟩−|βα00⟩). So shouldn't the CI coefficients be 0.704828210369 and -0.704828210369 instead of both being positive?
Posted Apr 2, 2026, 11:26 AM UTC