Anisotropic d-d Transition in Rutile TiO2

Wang, Tianjun1; Chen, Wei1,2; Xia, Shucai1,2; Ren, Zefeng1; Dai, Dongxu1; Yang, Xueming1,3; Zhou, Chuanyao1,2

2021-11-04

10.1021/acs.jpclett.1c02931

Journal of Physical Chemistry Letters   影响因子和分区

1948-7185

The band gap state of TiO2, which is dominated by Ti3+ 3d character, is of great relevance to light absorption, electron trapping, charge recombination, and conduction band structure. Despite the importance, the explanation of the excitation from this state is controversial. To this end, the electronic structures of TiO2(110) and TiO2(011)-(2 x 1) have been systematically measured with two-photon photoemission spectroscopy. The results reveal the anisotropic nature of the electronic structure in rutile TiO2 at seemingly equivalent directions of [110] and [1 (1) over bar0], the long axes of the TiO6 blocking unit. Although the resonant energy of these two d-d transitions is identical, the energy levels are systematically shifted by 0.1 eV. We propose this anisotropy originates from the broken symmetry of the rutile TiO2 crystals caused by the surface. The proposed asymmetry-caused electronic structure anisotropy could be generalized to other similar materials and may affect associated catalytic properties. This work provides an important benchmark for related calculations.

SCI ; EI

英语

NI论文

其他

National Natural Science Foundation of China[21973092,21688102] ; National Key Research and Development Program of China["2016YFA0200602","2018YFA0208703"] ; Strategic Pilot Science and Technology Project[XDB17000000]

Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics

Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Atomic, Molecular & Chemical

WOS:000716456200007

AMER CHEMICAL SOC

20214611145523

Crystal symmetry ; Electronic structure ; Energy gap ; Excited states ; Light absorption ; Oxide minerals ; Photoelectron spectroscopy ; Titanium dioxide

Minerals:482.2 ; Light/Optics:741.1 ; Inorganic Compounds:804.2 ; Physical Properties of Gases, Liquids and Solids:931.2 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4 ; Crystal Lattice:933.1.1

Web of Science

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

Wang, Tianjun,Chen, Wei,Xia, Shucai,et al. Anisotropic d-d Transition in Rutile TiO2[J]. Journal of Physical Chemistry Letters,2021,12(43):10515-10520.

Wang, Tianjun.,Chen, Wei.,Xia, Shucai.,Ren, Zefeng.,Dai, Dongxu.,...&Zhou, Chuanyao.(2021).Anisotropic d-d Transition in Rutile TiO2.Journal of Physical Chemistry Letters,12(43),10515-10520.

Wang, Tianjun,et al."Anisotropic d-d Transition in Rutile TiO2".Journal of Physical Chemistry Letters 12.43(2021):10515-10520.