A surface femtosecond two-photon photoemission （2PPE） spectrometer devoted to the study of ultrafast excited electron dynamics and photochemical kinetics on metal and metal oxide surfaces has been constructed. Low energy photoelectrons are measured using a hemispherical electron energy analyzer with an imaging detector that allows us to detect the energy and the angular distributions of the photoelectrons simultaneously. A Mach-Zehnder interferom- eter was built for the time-resolved 2PPE （TR-2PPE） measurement to study ultrafast surface excited electron dynamics, which was demonstrated on the Cu（111） surface. A scheme for measuring time-dependent 2PPE （TD-2PPE） spectra has also been developed for studies of surface photochemistry. This technique has been applied to a preliminary study on the photochemical kinetics on ethanol/TiO2（110）. We have also shown that the ultrafast dynamics of photoinduced surface excited resonances can be investigated in a reliable way by combining the TR-2PPE and TD-2PPE techniques.
任洋峰周传耀马志博肖春雷毛新春戴东旭Jerry LaRuebRussell CooperAlec M. Wodtke杨学明
As the photo-dissociation product of methanol on the TIO2（110） surface, the diffusion and desorption processes of formaldehyde （HCHO） were investigated by using scanning tunneling microscope （STM） and density functional theory （DFT）. The molecular-level images revealed the HCHO molecules could diffuse and desorb on the surface at 80 K under UV laser irra- diation. The diffusion was found to be mediated by hydrogen adatoms nearby, which were produced from photodissociation of methanol. Diffusion of HCHO was significantly decreased when there was only one H alatom near the HCHO molecule. Furthermore, single HCHO molecule adsorbed on the bare Ti02（l10） surface was quite stable, little photo-desorption was observed during laser irradiation. The mechanism of hydroxyl groups assisted diffusion of formaldehyde was also investigated using theoretical calculations.
The kinetics and dynamics of photocatalyzed dissociation of ethanol on TiO2（110） sur- face have been studied using the time-dependent and time-resolved femtosecond two-photon photoemission spectroscopy respectively, in order to unravel the photochemical properties of ethanol on this prototypical metal oxide surface. By monitoring the time evolution of the photoinduced excited state which is associated with the photocatalyzed dissociation of ethanol on Ti5c sites of Ti02（ll0）, the fractal-like kinetics of this surface photocatalytic reaction has been obtgined. The measured photocatalytic dissociation rate on reduced TiO2（l10） is faster than that on the oxidized surface. This is attributed to the larger defect density on the reduced surface which lowers the reaction barrier of the photocatalytic reaction at least methodologically. Possible reasons associated with the defect electrons for the acceleration have been discussed. By performing the interferometric two-pulse corre- lation on ethanol/TiO2（l10） interface, the ultrafast electron dynamics of the excited state has been measured. The analyzed lifetime （24 fs） of the excited state is similar to that on methanol/TiO2（110）. The appearance of the excited state provides a channel to mediate the electron transfer between the TiO2 substrate and its environment. Therefore studying its ultrafast electron dynamics may lead to the understanding of the microscopic mechanism of photocatalysis and photoelectrochemical energy conversion on TiO2.
The electronic structure of methanol/TiO2（ll0） interface has been studied by photoemis- sion spectroscopy. The pronounced resonance which appears at 5.5 eV above the Fermi level in two-photon photoemission spectroscopy （2PPE） is associated with the photocatalyzed dissociation of methanol at fivefold coordinated Ti sites （Ti5c） on TiO2 （110） surface [Chem- ical Science 1, 575 （2010）]. To check whether this resonance signal arises from initial or intermediate states, photon energy dependent 2PPE and comparison between one-photon photoemission spectroscopy and 2PPE have been performed. Both results consistently sug- gest the resonance signal originates from the initially unoccupied intermediate states, i.e., excited states. Dispersion measurements suggest the excited state is localized. Time-resolved studies show the lifetime of the excited state is 24 fs. This work presents comprehensive char- acterization of the excited states on methanol/TiO2（110） interface, and provides elaborate experimental data for the development of theoretical methods in reproducing the excited states on TiO2 surfaces and interfaces.
