We investigate by first-principles simulations the resonant electron-transfer
lifetime from the excited state of an organic adsorbate to a semiconductor
surface, namely isonicotinic acid on rutile TiO2(110). The
molecule-substrate interaction is described using density functional theory,
while the effect of a truly semi-infinite substrate is taken into account by
Green's function techniques. Excitonic effects due to the presence of
core-excited atoms in the molecule are shown to be instrumental to understand
the electron-transfer times measured using the so-called core-hole-clock
technique. In particular, for the isonicotinic acid on TiO2(110), we find
that the charge injection from the LUMO is quenched since this state lies
within the substrate band gap. We compute the resonant charge-transfer times
from LUMO+1 and LUMO+2, and systematically investigate the dependence of the
elastic lifetimes of these states on the alignment among adsorbate and
substrate states.Comment: 24 pages, 6 figures, to appear in Journal of Physical Chemistry
