Input for time-dependent density functional theory calculations follows very closely the input already described for the uncorrelated excited state methods described in the previous section (in particular, see Section 7.2.7). There are several points to be aware of:
The exchange and correlation functionals are specified exactly as for a ground state DFT calculation, through EXCHANGE and CORRELATION.
If RPA is set to TRUE, a “full” TDDFT calculation
will be performed, however the default value is RPA = FALSE,
which invokes the TDA,
Chem. Phys. Lett.
(1999), 314, pp. 291. in which the de-excitation amplitudes in Eq. (7.15) are neglected, which is usually a good approximation for excitation energies, although oscillator strengths within the TDA no longer formally satisfy the Thomas-Reiche-Kuhn sum rule. For RPA = TRUE, a TDA calculation is performed first and used as the initial guess for the full TDDFT calculation. The TDA calculation can be skipped altogether using RPA = 2
If SPIN_FLIP is set to TRUE when performing a TDDFT calculation, a SF-DFT calculation will also be performed. At present, SF-DFT is only implemented within TDDFT/TDA so RPA must be set to FALSE. Remember to set the spin multiplicity to 3 for systems with an even-number of electrons (e.g., diradicals), and 4 for odd-number electron systems (e.g., triradicals).
If MGGA_GINV is set to 1 when performing a TDDFT
calculation, gauge invariance correction will be added to MGGA
J. Chem. Phys.
(2012), 137, pp. 164105.