ABSTRACT
Measurements of the O-H and O-D vibrational lifetimes show that the room-temperature hydrogen diffusion rate in rutile TiO2 can be enhanced by 9 orders of magnitude when stimulated by resonant infrared light. We find that the local oscillatory motion of the proton quickly couples to a wag-mode-assisted classical transfer process along the c channel with a jump rate of greater than 1 THz and a barrier height of 0.2 eV. This increase in proton transport rate at moderate temperatures provides new insight into hydrogen transport in solids, which could play a role in applications ranging from fuel cells to hydrogen production.
ABSTRACT
The vibrational lifetimes of the O-H and O-D stretch modes in the perovskite oxide KTaO3 are measured by pump-probe infrared spectroscopy. Both stretch modes are exceptionally long lived and exhibit a large "reverse" isotope effect, due to a phonon-assisted proton-tunneling process, which involves the O-Ta-O bending motion. The excited-state tunneling rate is found to be 7 orders of magnitude larger than from the ground state in the proton conducting oxide, BaCeO3 [Phys. Rev. B 60, R3713 (1999)].
