Time-Dependent Density Functional Theory: Nonadiabatic Molecular Dynamics

Description

In recent decades, time-dependent density functional theory has been developed for computing excited-state properties of large-scale systems to high accuracy in biomolecules and nanomaterials, especially for ab initio nonadiabatic molecular dynamic simulations. It is therefore regarded as a most unique efficient method to do accurate simulation for large complex systems. This book compiles and details cutting-edge research in quantum chemistry and chemical physics from interdisciplinary groups from Japan, China, South Korea, the United States, Hong Kong, and Taiwan. These groups are developing excited-state dynamics methods involving conical intersections and intersystem crossings for large complex systems. Edited by Chaoyuan Zhu, a prominent chemical physics researcher, this book will appeal to anyone involved in molecular dynamics and spectroscopy, photochemistry, biochemistry, and materials chemistry research. Cover Half Title Title Page Copyright Page Table of Contents Preface Chapter 1: Intersystem Crossing Reaction for Fluorescent 10-Methyl-9(10H)-Acridone via Dioxetanone Intermediates: On-the-Fly Nonadiabatic ONIOM Molecular Dynamics with Particle Mesh Ewald Method and Thermodynamics Simulations 1.1: Introduction 1.2: Methodology 1.2.1: Electrostatic Potential from Quantum Mechanics 1.2.2: System Setup 1.2.3: Equilibration 1.2.4: ONIOM Potential Energies with Particle Mesh Ewald Method (PME-ONIOM) under a Periodic Boundary Condition 1.2.5: Spin–Orbit Coupling Calculation 1.2.6: Transition Probability for Intersystem Crossing 1.2.7: A Global Switching Algorithm 1.2.8: On-the-Fly PME-ONIOM Molecular Dynamics 1.3: Results and Discussion 1.3.1: Temperature Replica Exchange Molecular Dynamics Simulations 1.3.2: Electronic Structure Calculation with Electrostatic Embedding 1.3.3: On-the-Fly PME-ONIOM Molecular Dynamics 1.4: Summary Chapter 2: On-the-Fly Excited-State Molecular Dynamics Study Based on Spin-Flip Time-Dependent Density Functional Theory Approach: Photo-Branching Reaction of Stilbene and Stilbene Derivatives 2.1: Introduction 2.2: Spin-Flip Time-Dependent Density Functional Theory Approach for Excited-State Dynamics Simulation 2.3: Applications to Photoreaction of cis-SB, cis-DMSB, and cis-MSB in ππ* Excitation 2.3.1: Photoreaction of Stilbene 2.3.2: Geometries and Reaction Pathways on the ππ* Excited State of SB, dmSB, and mSB 2.3.3: Excited-State MD Simulations on Photo-Branching Reactions for SB, dmSB, and mSB 2.4: Concluding Remarks Chapter 3: Nonadiabatic Dynamics Simulations on the Excited States of Carbon-Related Materials with Time-Dependent Density Functional Theory 3.1: Introduction 3.1.1: Graphene-Based Luminescent Nanomaterials 3.1.2: Graphitic Carbon Nitride Photocatalyst 3.1.3: Applications of Excited-State Dynamics Simulations 3.2: Ground-State Structures and Absorption 3.3: Nonadiabatic Excited-State Simulations 3.4: Confirmation by Higher-Level Theoretical Method—Complete Active Space Self-Consistent Field 3.5: Summary Chapter 4: Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory as a Method of Choice for Nonadiabatic Molecular Dynamics 4.1: Introduction 4.2: Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory 4.2.1: Eliminating Spin-Contamination of SF-TDDFT 4.2.2: Combining Response States from Individual References 4.3: Performance Analysis of MRSF-TDDFT 4.3.1: Doubly Excited Configurations 4.3.2: Nonadiabatic Coupling Matrix Elements 4.3.3: Conical Intersections between S1 and S0 States (CI1/0) 4.3.4: Diradicals and Singet/Triplet Gap 4.3.5: Jahn–Teller Distortion 4.4: Nonadiabatic Molecular Dynamics 4.5: Conclusions Chapter 5: Conformationally Controlled Photochemistry Studied by Trajectory Surface Hopping 5.1: Introduction 5.2: Theoretical Methods 5.2.1: Generating Boltzmann Ensembles 5.2.2: Calculation of Absorption Spectra 5.2.3: Linear Response Time-Dependent Density Functional Surface Hopping 5.2.4: Prediction of Product Quantum Yields 5.3: Applications 5.3.1: Photochemistry of Z-Hexatriene Derivatives 5.3.2: Vitamin D Photochemistry 5.3.3: Wavelength-Dependent Product Quantum Yields in Z-Hexatriene Derivatives 5.4: Conclusion and Outlook Chapter 6: Generalized Trajectory-Based Surface-Hopping Nonadiabatic Dynamics with Time-Dependent Density Functional Theory: Methodologies and Applications 6.1: Theoretical Foundation of Nonadiabatic Effects 6.1.1: Breaking Down of Born–Oppenheimer Approximation 6.1.2: Nonadiabatic Molecular Dynamics 6.2: Generalized Trajectory Surface Hopping Method 6.2.1: Tully’s Fewest Switches Surface Hopping 6.2.2: Generalized Trajectory Surface Hopping Method 6.2.3: Generalized Trajectory Surface Hopping Method at QM/MM Level 6.2.4: Algorithm and Implementation of the Generalized Trajectory Surface Hopping Method 6.3: Generalized Trajectory Surface Hopping Method with Frequency-Domain Time-Dependent Density Functional Theory Method 6.3.1: Linear Response Time-Dependent Density Functional Theory 6.3.2: Generalized Trajectory Surface Hopping Method at Linear Response Time-Dependent Density Functional Theory Level 6.3.3: Applications 6.4: Generalized Trajectory-Based Surface-Hopping Method with Time-Domain Time-Dependent Density Functional Theory Method 6.4.1: Time-Domain Time-Dependent Density Functional Theory 6.4.2: Generalized Trajectory-Based Surface-Hopping at Time-Domain Time-Dependent Density Functional Theory Level 6.4.3: Applications with Collinear and Noncollinear DFT Methods 6.5: Conclusion and Perspective Chapter 7: Multistate Nonadiabatic Molecular Dynamics: The Role of Conical Intersection between the Excited States 7.1: Introduction 7.2: Theory and Methods 7.3: Results and Discussion 7.3.1: Wavelength-Dependent Photoisomerization Quantum Yield 7.3.2: Vibronic Interaction between the Close-Lying ππ* and nπ* States 7.3.3: Minimal Energy Conical Intersection between Locally Excited and Charge Transfer States 7.4: Summary and Outlook Chapter 8: Excited Carrier Dynamics in Condensed Matter Systems Investigated by ab initio Nonadiabatic Molecular Dynamics 8.1: Introduction 8.2: Time-Dependent Kohn–Sham Equation Combined with Surface Hopping 8.3: Interfacial Charge Transfer Dynamics 8.3.1: Charge Transfer at Molecule/Semiconductor 8.3.1.1: Ultrafast photoexcited hole transfer at CH3OH/TiO2 interface 8.3.1.2: CO2 photoreduction on TiO2 driven by transient capture of photoexcited electron 8.3.2: Charge Transfer at van der Waals Heterostructure 8.3.2.1: Phonon-assisted ultrafast charge transfer at MoS2/WS2 8.3.2.2: Phonon-coupled charge oscillation at MoSe2/WSe2 8.3.2.3: Control the charge transfer dynamics at MoS2/WS2 by external stress 8.3.2.4: Comparing with other works 8.4: Electron–Hole Recombination in Semiconductors 8.4.1: Electron–Hole Recombination in TiO2 8.4.2: Electron–Hole Recombination in Halide Perovskite 8.4.3: Electron–Hole Recombination in 2D Materials 8.5: Exciton Dynamics 8.5.1: GW+Real-Time BSE NAMD Method 8.5.2: Spin Valley Exciton Dynamics in MoS2 8.6: Summary and Perspectives Chapter 9: Time-Dependent Density Matrix Renormalization Group for Quantum Chemistry 9.1: Introduction 9.2: Matrix Product State, Density Matrix Renormalization Group 9.2.1: Matrix Product State and Matrix Product Operator 9.2.2: Density Matrix Renormalization Group 9.3: Time-Dependent Density Matrix Renormalization Group 9.3.1: The Runge–Kutta Approaches 9.3.2: The Krylov Subspace Approach 9.3.3: The Time-Evolving Block Decimation Methods 9.3.4: The Time-Dependent Variational Principle Method 9.4: Examples 9.4.1: A General Exciton-Vibration Model for Chemistry Systems 9.4.2: Charge Carrier Dynamics in Polymer Chain 9.4.3: Exciton Dissociation at Donor/Acceptor Interface 9.4.4: Excited State Charge Transfer 9.4.5: Photo-Dynamics and Absorption Spectrum for Pyrazine 9.4.6: Singlet Fission 9.5: Summary and Outlook Chapter 10: Spin-Flip TDDFT for Photochemistry 10.1: Computational Photochemistry 10.1.1: Conical Intersections 10.1.2: Time-Dependent DFT 10.2: Spin-Flip TDDFT Approach 10.2.1: Theory 10.2.1.1: Conceptual overview 10.2.1.2: Formalism 10.2.1.3: Nonadiabatic (derivative) couplings 10.2.2: Photochemical Applications 10.2.2.1: Exploring excited-state potential surfaces 10.2.2.2: Trajectory surface hopping 10.2.2.3: Spin contamination and state tracking 10.3: Augmented Spin-Flip Methods 10.3.1: Spin-Adapted Spin-Flip Approach 10.3.1.1: Formalism 10.3.1.2: Applications 10.3.2: Mixed-Reference Spin-Flip Approach 10.3.2.1: Formalism 10.3.2.2: Applications 10.4: Summary and Outlook Chapter 11: Phase Space Mapping Theory for Nonadiabatic Quantum Molecular Dynamics 11.1: Introduction 11.1.1: Nonadiabatic Dynamics in the Wavefunction Picture 11.1.2: Nonadiabatic Dynamics with the Density Operator 11.2: Unified Phase Space Formulation for both Nuclear and Electronic Freedoms 11.2.1: Meyer–Miller Mapping Hamiltonian Model 11.2.2: Unified Formulation of Mapping Phase Space 11.3: Trajectory-Based Approaches 11.3.1: Extended Classical Mapping Model 11.3.2: Equations of Motion in the Adiabatic Representation 11.3.3: Ehrenfest Dynamics and Surface Hopping 11.4: Applications 11.4.1: Spin-Boson Model in Condensed Phase 11.4.2: Tully’s Gas Phase Scattering Models 11.4.3: Atom-in-Cavity Models 11.5: Concluding Remarks Chapter 12: Global Switch Trajectory Surface Hopping Dynamics in the Framework of Time-Dependent Density Functional Theory 12.1: Introduction 12.2: Global Switch Trajectory Surface Hopping Dynamics 12.2.1: Time-Dependent Scheme and Local Switch Probability 12.2.2: Time-Independent Scheme and Global Switch Probability 12.2.3: Velocity Adjustment 12.2.4: Implementation of Global Switch Algorithm 12.3: The Performance of Global Switch Versus Local Switch 12.3.1: Photoisomerization of Azobenzene on S1-(n, π*) Excitation 12.3.2: Hopping Spots, Switching Probabilities and Velocity Adjustment 12.4: The Performance of Time-Dependent Density Functional Theory in Global Switch Algorithm 12.4.1: Topology of S0 and S1 PESs Around Conical Intersections 12.4.2: GS-TSH-MD Simulations by Time-Dependent Density Functional Theory with and without Spin-Flip 12.5: Time-Dependent Density Functional Theory Functional and Basis Set Dependence in GS-TSH-MD Simulation 12.5.1: Functional and Basis Set Dependence on Artificial Double Cone 12.5.2: Functional and Basis Set Dependence on Dynamic Quantities 12.6: GS-TSH-MD Simulation for Chemiluminescence 12.6.1: Electron Transfer Catalyzed Chemiluminescence of Luminol 12.6.2: Uncatalyzed Chemiluminescence of Methylated 1,2-dioxetane 12.7: GS-TSH-MD Simulation for Photoisomerization of dMe-OMe-NAIP 12.7.1: Time-Dependent Density Functional Theory Calculations for Searching Conical Intersections 12.7.2: Both E-to-Z and Z-to-E Photoisomerization in GS-TSH-MD Simulation Index