I am trying to model a single electron transfer (SET) mechanism at density functional theory (DFT) level of theory.
that molecular object are you investigating?
it may be efficient to calculate electrostatic potential
or relative energy of complexes with different electron location
or location of HOMO, LUMO electrons
Well most direct route would be to optimize molecule in initial and final electronic state separately then try to use QST2 or QST3 (providing that you have good guess about transition state). All this will work providing that you can find stable geometry for both electronic states and the intersection of both electronic state PES has larger gap. If not you have to ask specialist of conical intersection (avoided crossing if spin state of both electronic isomers is the same) detection to give you tips how to find it on PES. If you cannot optimize geometry of upper energy state you can check electronic spectrum using TD-DFT because it is quite likely that for inner-sphere electron transfer for distant Donor-Acceptor system this transition might be of lowest energy from all electronic transition or at least very close to Lowest ET. Best is to look on electronic density maps of those few transitions to decide which corresponds to relocation of electronic density toward acceptor atom/group. This should give you some idea about energy threshold faced by SET but again it is the best to optimize geometry for both states to get energy difference that is approximation of SET reaction Gibbs energy (delta)G.
are you trying to calculate excitation energy? If you are using gaussian09 then you can do it with guess=(read,alter) keyword.
Its not an excitation energy calculation its an electron transfer from a metal center entity to a ligated reactive molecule, thanks.
Well many intramolecular ET is manifested by presence of CT bands in this case MLCT bands. You should revisit Marcus theory and other researchers conclusions concerning rates of outer sphere electron transfer reactions. It is not the case but mathematical apparatus and conclusions are in large extent applicable for intramolecular ET.
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