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Deuterium Kinetic Isotope Effect in the Photocatalyzed Dissociation of Methanol on TiO2(110)
摘要： Deuterium kinetic isotope effect (KIE) in the photochemistry of methanol on TiO2(110) has been studied to find the rate-determining step (RDS) and understand the reaction mechanism using two-photon photoemission spectroscopy (2PPE). Deuterium substitution of the methyl hydrogen has little effect on the kinetics of this reaction, suggesting that neither the break of the C-H(D) bond nor the transfer of H(D) atoms to the bridging sites is the RDS in the transformation of methanol into formaldehyde. In contrast, the reaction rate of MeOH is ~1.3 times of that of MeOD, suggesting that the cleavage of O-H(D) is the RDS in the photocatalyzed dissociation of methanol on TiO2(110). The results contradict with the common fact that C-H(D) is more difficult to break than O-H(D) based on ground state energetics, implying the involvement of photogenerated charge carriers in the reaction of C-H break whereas the cleavage of O-H is likely a thermal reaction. Difference in the activation energy of O-H and O-D dissociation reaction in the methanol/TiO2(110) system has been calculated based on the KIE measurements. Our work is consistent with the fact that methoxy is photocatalytically more reactive than methanol, and suggests that the conversion of methanol into methoxy is crucial in the photochemistry of methanol on TiO2(110) and probably other metal oxide semiconductor surfaces.
关键词： two-photon photoemission spectroscopy,photocatalyzed dissociation,Deuterium kinetic isotope effect,TiO2(110),methanol
更新于2025-09-23 15:21:01
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surface alloy
摘要： We have investigated the atomic and electronic structure of the (√3×√3)R30? SnAu2/Au(111) surface alloy. Low-energy electron diffraction and scanning tunneling microscopy measurements show that the native herringbone reconstruction of bare Au(111) surface remains intact after formation of a long-range ordered (√3×√3)R30? SnAu2/Au(111) surface alloy. Angle-resolved photoemission and two-photon photoemission spectroscopy techniques reveal Rashba-type spin-split bands in the occupied valence band with comparable momentum space splitting as observed for the Au(111) surface state, but with a hole-like parabolic dispersion. Our experimental findings are compared with density functional theory (DFT) calculation that fully support our experimental findings. Taking advantage of the good agreement between our DFT calculations and the experimental results, we are able to extract that the occupied Sn-Au hybrid band is of (s, d )-orbital character, while the unoccupied Sn-Au hybrid bands are of (p, d )-orbital character. Hence we can conclude that the Rashba-type spin splitting of the hole-like Sn-Au hybrid surface state is caused by the significant mixing of Au d with Sn s states in conjunction with the strong atomic spin-orbit coupling of Au, i.e., of the substrate.
关键词： angle-resolved photoemission spectroscopy,density functional theory,SnAu2/Au(111) surface alloy,Rashba-type spin splitting,two-photon photoemission spectroscopy
更新于2025-09-09 09:28:46
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Hybridization of an unoccupied molecular orbital with an image potential state at a lead phthalocyanine/graphite interface
摘要： The interaction of a molecular orbital with a surface state is important to understand the spatial distribution of the wave function at the molecule/substrate interface. In this study, we focus on hybridization of an unoccupied state of lead phthalocyanine (PbPc) with the image potential state (IPS) on a graphite surface. The hybridization modifies the energy-momentum dispersions of the IPS on PbPc films as observed by angle-resolved two-photon photoemission. On the PbPc 1 monolayer film, the IPS band forms a band gap and back-folding appears at the first Brillouin zone boundary due to the periodic potential by the adsorbate lattice. The modification of the dispersion is accompanied by the intensity enhancement of the IPS. We attributed the origin of the modified dispersion and intensity enhancement to a hybridization of the IPS with a molecule-derived unoccupied level. From the photon energy-dependent measurement on multilayer films, we have found the diffuse unoccupied molecular level in the vicinity of the IPS. The tail part of the IPS wave function in the substrate is enhanced by the hybridization with the unoccupied state, and thus strengthens the transition from the occupied substrate band to the hybridized IPS.
关键词： organic ultrathin films,image potential states,two-photon photoemission spectroscopy,unoccupied states,hybridization
更新于2025-09-04 15:30:14