Site-Selective Excitation of Ti³⁺ Ions in Rutile TiO₂ via Anisotropic Intra-Atomic 3d â 3d Transition

Li, Jialong1,2; Wang, Tianjun2; Xia, Shucai2; Chen, Wei2,3; Ren, Zefeng2; Sun, Min1; Che, Li1; Yang, Xueming2,4; Zhou, Chuanyao2,3

2024-01-17

10.1021/jacsau.3c00600

JACS AU   影响因子和分区

2691-3704

Site-selective excitation (SSE), which is usually realized by tuning the wavelength of absorbed light, is an ideal way to study bond-selective chemistry, analyze the crystal structure, investigate protein conformation, etc., eventually leading to active manipulation of desired processes. Herein, SSE has been explored in (110)-, (100)-, and (011)-faced rutile TiO2, a prototypical material in both surface science and photocatalysis fields. Using ultraviolet photoelectron spectroscopy and photon energy-, substrate orientation-, and laser polarization-dependent two-photon photoemission spectroscopy (2PPE), intra-atomic 3d -> 3d transition from the split Ti3+ 3d orbitals, i.e., band gap states and excited states at similar to 1.00 eV below and similar to 2.40 eV above the Fermi level, respectively, has been proven for all of the samples, suggesting that it is a common property of this material. The distinct structure of rutile TiO2 results in the anisotropic 3d -> 3d transitions with the transition dipole moment along the long axes ([110] and [110]) of TiO6 blocking units. This anisotropy facilitates the selective excitation of Ti3+ ions in the two types of TiO6, which cannot be realized by conventional wavelength tuning, via polarization alignment of the excitation source. Discovery in this work builds the foundation for future investigation of site-selective photophysical and photochemical processes and eventually possible active manipulation in this material at the atomic level.

site-selective excitation (SSE) rutile TiO2 anisotropic intra-atomic d -> d transition atom-specific photophysics and photochemistry two-photonphotoemission spectroscopy (2PPE)

ESCI

英语

其他

National Natural Science Foundation of China[2021YFA1500601] ; National Key Research and Development Program of China["22322306","21973092","22288201","21973010"] ; National Natural Science Foundation of China[YSBR-007] ; Chinese Academy of Sciences[XLYC1907032]

Chemistry

Chemistry, Multidisciplinary

WOS:001162253500001

AMER CHEMICAL SOC

Web of Science

1.Dalian Maritime Univ, Sch Sci, Dept Phys, Dalian 116026, Peoples R China
2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
3.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
4.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China

Li, Jialong,Wang, Tianjun,Xia, Shucai,et al. Site-Selective Excitation of Ti³⁺ Ions in Rutile TiO₂ via Anisotropic Intra-Atomic 3d â 3d Transition[J]. JACS AU,2024,4(2).

Li, Jialong.,Wang, Tianjun.,Xia, Shucai.,Chen, Wei.,Ren, Zefeng.,...&Zhou, Chuanyao.(2024).Site-Selective Excitation of Ti³⁺ Ions in Rutile TiO₂ via Anisotropic Intra-Atomic 3d â 3d Transition.JACS AU,4(2).

Li, Jialong,et al."Site-Selective Excitation of Ti³⁺ Ions in Rutile TiO₂ via Anisotropic Intra-Atomic 3d â 3d Transition".JACS AU 4.2(2024).