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Time-dependent Nonadiabatic Investigations on the Photo-generated Carrier Dynamics at TiO2/molecule Interfaces


EMSL Project ID
48900

Abstract

Band gap excitation of TiO2 instigates photocatalytic reactions. In the presence of molecular adsorbates the generated holes and electrons act as the reactants in the oxidation and reduction processes for solar fuel generation. In order to understand photocatalytic processes through theoretical methods one must go beyond theoretical descriptions of the static molecular end electronic structure, because the nuclear and electronic interactions leading to chemistry are strongly coupled. We propose to carry out ab initio theoretical investigations on dynamics of photogenerated holes and electrons based on time-dependent nonadiabatic molecular dynamics (NAMD) method. We will focus on the H2O/TiO2, CH3OH/TiO2 and CO2/TiO2 chemisorption systems, which are tractable by theory and for which extensive chemical, STM, and time-resolved two photon photoemission (TR-2PP) studies exist. We plan to study the interfacial transfer and decay dynamics of photogenerated carriers. The coupling with phonons and proton transfer will be also investigated. The proposed theoretical research will couple strongly with the ongoing TR-2PP spectroscopy experiments at the University of Pittsburgh.
The research on photocatalytic processes at metal oxide surfaces is directed to the clean and sustainable energy generation, environmental remediation, and climate change. The research addresses CESD goals to 1) strengthen model representations of energy and other human systems such as dynamic emissions; 2) advance understanding and process representation of the couplings involving energy, carbon, and water cycles; and 3) to use of EMSL high-performance computing to characterization and understanding of the experimental and theoretical basis of molecular-level reactions that occur in energy transduction and carbon recapture systems. The results of the proposed research are likely to have an impact on the fundamental molecular science for reducing the human impact on global climate and environment.
For the proposed NAMD simulations, usually we need to perform an ab initio molecular dynamics calculation up to 10 ps, which means 10,000 steps of electronic structure optimization. And for different structures and initial conditions, we need to perform many such calculations. Therefore, we believe the supercomputing facilities at EMSL are essential for our large scale computing needs. Neither PI has in-house computing facilities that could accomplish the proposed research. We request 150,000 node-hrs computing time on the Cascade supercomputer for the planned theoretical studies.

Project Details

Project type
Large-Scale EMSL Research
Start Date
2015-10-01
End Date
2017-09-30
Status
Closed

Team

Principal Investigator

Hrvoje Petek
Institution
University of Pittsburgh

Co-Investigator(s)

Jin Zhao
Institution
University of Science and Technology of China, Chinese Academy of Sciences

Team Members

Yanan Wang
Institution
University of Science and Technology of China, Chinese Academy of Sciences

Lili Zhang
Institution
University of Science and Technology of China, Chinese Academy of Sciences

Cong Wang
Institution
University of Pittsburgh

Weibin Chu
Institution
University of Science and Technology of China, Chinese Academy of Sciences

Liming Liu
Institution
University of Science and Technology of China, Chinese Academy of Sciences

Yongliang Shi
Institution
University of Science and Technology of China, Chinese Academy of Sciences

Hongli Guo
Institution
California State University, Northridge

Hao Sun
Institution
University of Pennsylvania

Huijuan Sun
Institution
University of Science and Technology of China, Chinese Academy of Sciences

Qijing Zheng
Institution
University of Science and Technology of China, Chinese Academy of Sciences

Related Publications

Chen KD, Y Shi, and J Zhao. 2015. "Oxidation of Anatase TiO2(001) (1x4) Surface." Chinese Journal of Chemical Physics 28(6):664. doi:10. 1063/1674-0068/28/cjcp1505095
Chu W ,Al-Saidi W A,Zheng Q ,Xie Y ,Lan Z ,Prezhdo O ,Petek H ,Zhao J 2016. "Ultrafast Dynamics of Photongenerated Holes at a CH3OH/TiO2 Rutile Interface" Journal of the American Chemical Society 138(41):13740–13749. 10.1021/jacs.6b08725
Guo H ,Al-Saidi W A,Zhao J 2016. "Tunability of the Two-dimensional Electron Gas at the LaAlO3/SrTiO3 Interface by Strain-induced Ferroelectricity" Physical Chemistry Chemical Physics. PCCP 18(41):28474-28484. 10.1039/C6CP04769F
Guo H., C. Zhao, Q. Zheng, Z. Lan, O. Prezhdo, W.A. Al-Saidi, and J. Zhao. 2018. "Superatom Molecular Orbital as an Interfacial Charge Separation State." Journal of Physical Chemistry Letters 9, no. 12:3485–3490. doi:10.1021/acs.jpclett.8b01302
Guo H, WA Al-Saidi, J Yang, and J Zhao. 2016. "Nano-scale Polar–nonpolar Oxide Heterostructures for Photocatalysis." Nanoscale 8(11):6057-6063. doi:10. 1039/c5nr08689b
Liu L ,Zhao J 2016. "Formaldehyde Adsorption and Decomposition on Rutile (110): A First-Principles Study" Surface Science 62():156–162. 10.1016/j.susc.2015.12.036
Shi Y., B. Song, R. Shahbazian-Yassar, J. Zhao, and W.A. Al-Saidi. 2018. "Experimentally Validated Structures of Supported Metal Nanoclusters on MoS2." Journal of Physical Chemistry Letters 9, no. 11:2972–2978. doi:10.1021/acs.jpclett.8b01233
Shi Y., H. Sun, M. Nguyen, C. Wang, K. Ho, W.A. Al-Saidi, and J. Zhao. 2017. "Structures of Defects on Anatase TiO2(001) Surfaces." Nanoscale 9, no. 32:11553. doi:10.1039/c7nr02458d
Shi Y., H. Sun, W.A. Al-Saidi, M. Nguyen, C. Wang, K. Ho, and J. Yang, et al. 2017. "Role of Surface Stress on the Reactivity of Anatase TiO2(001)." Journal of Physical Chemistry Letters 8, no. 8:1764–1771. doi:10.1021/acs.jpclett.7b00181
Sun H ,Li B ,Zhao J 2016. "Half-metallicity in 2D Organometallic Honeycomb Frameworks" Journal of Physics: Condensed Matter 28():425301. 10.1088/0953-8984/28/42/425301
Sun H ,Zhao J 2016. "New Family of Dirac and Weyl Semimetals in XAuTe (X = Na, K, Rb) Ternary Honeycomb Compounds" Science China. Physics, Mechanics & Astronomy 59():107011. 10.1007/s11433-016-0174-6
Tan S., A. Argondizzo, J. Ren, L. Liu, J. Zhao, and H. Petek. 2017. "Plasmonic Coupling at a Metal/Semiconductor Interface." Nature Photonics 11. doi:10.1038/s41566-017-0049-4
Tan S ,Liu L ,Dai Y ,Ren J ,Zhao J ,Petek H 2017. "Ultrafast Plasmon-Enhanced Hot Electron Generation at Ag Nanocluster/Graphite Heterojunctions" Journal of the American Chemical Society
Tan S., L. Liu, Y. Dai, J. Ren, J. Zhao, and H. Petek. 2017. "Ultrafast Plasmon-Enhanced Hot Electron Generation at Ag Nanocluster/Graphite Heterojunctions." Journal of the American Chemical Society. doi:10.1021/jacs.7b01079
Tan S., Y. Dai, S. Zhang, L. Liu, J. Zhao, and H. Petek. 2018. "Coherent Electron Transfer at the Ag/Graphite Heterojunction Interface." Physical Review Letters 120. doi:10.1103/PhysRevLett.120.126801
Wang Y., H. Guo, Q. Zheng, W.A. Al-Saidi, and J. Zhao. 2018. "Tuning Solvated Electrons by Polar-Nonpolar Oxide Heterostructure." Journal of Physical Chemistry Letters 9, no. 11:3049–3056. doi:10.1021/acs.jpclett.8b00938
Zhang L., Q. Zheng, Y. Xie, Z. Lan, O. Prezhdo, W.A. Al-Saidi, and J. Zhao. 2018. "Delocalized Impurity Phonon Induced Electron-Hole Recombination in Doped Semiconductors." Nano Letters 18, no. 3:1592–1599. doi:10.1021/acs.nanolett.7b03933
Zhang S, C Wang, X Cui, Y Wang, A Argondizzo, J Zhao, and H Petek. 2016. "Time-resolved Photoemission Study of the Electronic Structure and Dynamics of Chemisorbed Alkali Atoms on Ru(0001)." Physical Review B 93(4):045401. doi:10. 1103/PhysRevB. 93. 045401
Zhao C., Q. Zheng, J. Wu, and J. Zhao. 2017. "Ab Initio Nonadiabatic Molecular Dynamics Investigation on the Dynamics of Photogenerated Spin Hole Current in Cu-doped MoS2." Physical Review B 96, no. 13:134308. doi:10.1103/PhysRevB.96.134308
Zheng Q., W.A. Al-Saidi, Y. Xie, Z. Lan, O. Prezhdo, H. Petek, and J. Zhao. 2017. "Phonon-Assisted Ultrafast Charge Transfer at van der Waals Heterostructure Interface." Nano Letters 17, no. 10:6435–6442. doi:10.1021/acs.nanolett.7b03429
Zheng Q., Y. Xie, Z. Lan, O. Prezhdo, W.A. Al-Saidi, and J. Zhao. 2018. "Phonon-coupled Ultrafast Interlayer Charge Oscillation at Van der Waals Heterostructure Interfaces." Physical Review B 97. doi:10.1103/PhysRevB.97.205417
Zheng Q., Y. Xie, Z. Lan, O. Prezhdo, W.A. Al-Saidi, and J. Zhao. 2018. "Phonon-coupled Ultrafast Interlayer Charge Oscillation at Van der Waals Heterostructure Interfaces." Physical Review B 97. doi:10.1103/PhysRevB.97.205417