Spin-flip excitation energies [156,157] can only be obtained in a spin-unrestricted TDDFT calculation. This can not be used in case of spin-orbit coupling. At present, the spin-flip excitation energies can only be calculated with Tamm-Dancoff approximation (TDA) [158] and Davidson's method.
To calculate spin-flip excitation energies, one must specify two keys:
SFTDDFT
and
TDA
anywhere in the input file in addition to the EXCITATION block keyword.
In spin-flip TDDFT, the XC kernel can be calculated directly from the XC potential. To use the LDA potential for the XC kernel, which roughly corresponds to the ALDA in ordinary TDDFT, one must specify the key
FORCEALDA
anywhere in the input file. Only calculations using the LDA potential in the SCF are fully tested. Using other GGA potentials in the SCF and using the FORCEALDA key at the same time may introduce unreasonable results, while using LB94 or SAOP potential in the SCF without the FORCEALDA key may give unstable results. Unstable results have been reported for the PW91 functional.
For open-shell molecules, spin-flip transition can result in transition to the ground state with a different Sz value, while the symmetry of the transition density is A1. The excitation energy of this transition should be zero and this can be used to test the reliability of spin-flip TDDFT.
The symmetry of the excited states can be determined in the same way as that in spin-unrestricted TDDFT calculations. As for the spin state, similar to that in the spin-unrestricted TDDFT calculations, some states may be more or less pure spin states, others may just be mixtures. The users can interpret the excited state through the transitions that contribute to this state. Note that the transitions are always from α spin-orbital to β spin-orbital in spin-flip calculations, or from β spin-orbital to α spin-orbital.
