Excited states equilibrium geometries

If the ligand field parameter Dq of the relaxed (at equilibrium) excited state is available from the evaluation of excited state spectra a similar set of formulas can be derived. The ligand field parameters for the ground state and excited state equilibrium geometry Dq and Dq, respectively, (cf. Fig. 1) are related for the one-electron case d using the parabolic formula and Eq. (17) by... 

Standard wavefunction methods (i.e., other than DFT), which have been extensively applied both to the computation of vertical (i.e., at ground state equilibrium geometry) excitation energies and excited state reaction paths are the current preferred method for applications in this field. Wavefunction methods that are used in studying photochemical mechanisms are limited to those that can describe excited states correctly. Unfortunately, standard methods for the evaluation of the ground state PES such as SCF and DFT cannot describe excited states because they are restricted to the aufbau principle. 

The analysis of the photochemical activity of nuclear coordinates is now presented in more details. Most of the formalism has been presented in [31]. The analysis presented in Section 2 is generalized here to the ground-state equilibrium geometry (i.e., FC point in the excited state), where the energy difference is not zero. 

Figure 15. Harmonic-excited-state Bom-Oppenheimer potential energy surface. The classical trajectory that originates at rest from the ground-state equilibrium geometry is shown superimposed. 

Figure 24. (a) Anhannonic excited-state potential energy surface. The classical trajectory that originates from rest from the ground-state equilibrium geometry is shown superposed. (b) Probability (0 or 1) of exit from channel I as a function of excited-state propagation time, (c) Same as (b), only for exit channel 2. 

---