Non-Adiabatic Molecular Dynamics Methods for Materials Discovery [electronic resource]

• Ngôn ngữ: eng
• Ký hiệu phân loại: 333.79 Energy
• Thông tin xuất bản: Washington, D.C. : Oak Ridge, Tenn. : United States. Dept. of Energy. Office of Science ; Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy, 2017
• Mô tả vật lý: Size: 4 p. : , digital, PDF file.
• Bộ sưu tập: Metadata
• ID: 255754
• Chủ đề: 1. 14 solar energy; 2. 30 direct energy conversion; 3. 36 materials science; 4. 37 inorganic, organic, physical, and analytical chemistry; 5. 74 atomic and molecular physics; 6. 97 mathematics and computing; 7. Et al; 8. Excited states; 9. Non-adiabatic molecular dynamics; 10. Response theory; 11. Time-dependent density functional theory

Tóm tắt

The flow of radiative energy in light-driven materials such as photosensitizer dyes or photocatalysts is governed by non-adiabatic transitions between electronic states and cannot be described within the Born-Oppenheimer approximation commonly used in electronic structure theory. The non-adiabatic molecular dynamics (NAMD) methods based on Tully surface hopping and time-dependent density functional theory developed in this project have greatly extended the range of molecular materials that can be tackled by NAMD simulations. New algorithms to compute molecular excited state and response properties efficiently were developed. Fundamental limitations of common non-linear response methods were discovered and characterized. Methods for accurate computations of vibronic spectra of materials such as black absorbers were developed and applied. It was shown that open-shell TDDFT methods capture bond breaking in NAMD simulations, a longstanding challenge for single-reference molecular dynamics simulations. The methods developed in this project were applied to study the photodissociation of acetaldehyde and revealed that non-adiabatic effects are experimentally observable in fragment kinetic energy distributions. Finally, the project enabled the first detailed NAMD simulations of photocatalytic water oxidation by titania nanoclusters, uncovering the mechanism of this fundamentally important reaction for fuel generation and storage.