Time-Dependent Density. Functional Theory Nonadiabatic Molecular Dynamics

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