This book focuses on current applications of molecular quantum dynamics. Examples from all main subjects in the field, presented by the internationally renowned experts, illustrate the importance of the domain. Recent success in helping to understand experimental observations in fields like heterogeneous catalysis, photochemistry, reactive scattering, optical spectroscopy, or femto- and attosecond chemistry and spectroscopy underline that nuclear quantum mechanical effects affect many areas of chemical and physical research. In contrast to standard quantum chemistry calculations, where the nuclei are treated classically, molecular quantum dynamics can cover quantum mechanical effects in their motion. Many examples, ranging from fundamental to applied problems, are known today that are impacted by nuclear quantum mechanical effects, including phenomena like tunneling, zero point energy effects, or non-adiabatic transitions. Being important to correctly understand many observations in chemical, organic and biological systems, or for the understanding of molecular spectroscopy, the range of applications covered in this book comprises broad areas of science: from astrophysics and the physics and chemistry of the atmosphere, over elementary processes in chemistry, to biological processes (such as the first steps of photosynthesis or vision). Nevertheless, many researchers refrain from entering this domain. The book "Molecular Quantum Dynamics" offers them an accessible introduction. Although the calculation of large systems still presents a challenge - despite the considerable power of modern computers - new strategies have been developed to extend the studies to systems of increasing size. Such strategies are presented after a brief overview of the historical background. Strong emphasis is put on an educational presentation of the fundamental concepts, so that the reader can inform himself about the most important concepts, like eigenstates, wave packets, quantum mechanical resonances, entanglement, etc. The chosen examples highlight that high-level experiments and theory need to work closely together. This book thus is a must-read both for researchers working experimentally or theoretically in the concerned fields, and generally for anyone interested in the exciting world of molecular quantum dynamics.
Author(s): Fabien Gatti
Publisher: Springer
Year: 2014
Language: English
Pages: 273
Foreword
Preface
Contents
1 Introduction and Conceptual Background
References
2 Elementary Molecule–Surface Scattering Processes Relevant to Heterogeneous Catalysis: Insights from Quantum Dynamics Calculations
2.1 Introduction
2.2 Reactive and Nonreactive Scattering of Molecules from Metal Surfaces
2.2.1 H2/Metal Surfaces
2.2.1.1 Non-activated Systems
2.2.1.2 Activated Systems
2.2.2 CH4/Metal Surfaces
2.3 Conclusions and Outlook
References
3 Tunneling in Unimolecular and Bimolecular Reactions
3.1 Introduction
3.2 Photodissociation of NH3
3.3 OH+CO=→H+CO2 Reaction
3.4 Conclusions
References
4 Reactive Scattering and Resonance
4.1 Introduction
4.2 Resonance in a Reactive Scattering
4.3 Theory by Quantum Wave Packet Method
4.3.1 Overall Theory
4.3.2 Quantum Wave Packet Method
4.3.2.1 Hamiltonian and Discretization
4.3.2.2 Construction of the Initial Wave Packet
4.3.2.3 Propagation of the Wave Packet
4.3.3 State-to-State Method: The RPD Approach
4.3.4 Calculation of the Experimental Observations
4.3.4.1 Calculation of S-Matrix of Triatomic Reaction Using the RCB Method
4.3.4.2 Calculation of ICS and DCS
4.3.4.3 Calculation of Reaction Rate
4.3.4.4 Calculation and Characterization of the Reactive Resonance Wavefunction
4.4 Applications
4.4.1 Resonances in F Plus H2 and Its Isotopes
4.4.2 Non-statistical Effects in H+O2 Reaction
4.4.3 H2+OH
4.4.4 OH+CO
4.5 Conclusion
References
5 Vibrational Spectroscopy and Molecular Dynamics
5.1 Introduction
5.2 High-Dimensional Quantum Dynamics
5.3 Infrared Spectroscopy and Dynamics of the Protonated Water Dimer
5.3.1 Infrared Spectroscopy
5.3.2 Dynamics of the Excess Proton
5.4 Tunneling Splitting of Malonaldehyde
5.4.1 Calculated State Energies
5.5 Summary
References
6 Vibronic Coupling Effects in Spectroscopy and Non-adiabatic Transitions in Molecular Photodynamics
6.1 General Introduction
6.1.1 Outline of Early History
6.1.2 Methodology and Phenomena
6.1.2.1 Diabatic Electronic States
6.1.2.2 Classification of Two-State Intersections
6.1.2.3 Dynamics at Conical Intersections
6.1.2.4 Two-State vs. Three-State Coupling Scenarios
6.1.2.5 Vibronic Coupling and Localization Phenomena
6.2 Applications in Spectroscopy
6.3 Applications in Photophysics and Photochemistry
6.3.1 Ultrafast Internal Conversion and Its Competition with Fluorescence
6.3.2 Elementary Photochemical Transformations
6.4 Outlook and Future Perspectives
References
7 Non-adiabatic Photochemistry: Ultrafast Electronic State Transitions and Nuclear Wavepacket Coherence
7.1 Introduction
7.2 Classifying Conical Intersections: Shapes and Positions
7.3 Simulating Non-adiabatic Transitions
7.3.1 Grid-Based Quantum Dynamics
7.3.2 Gaussian-Based Quantum Dynamics
7.3.3 Trajectory-Based Semi-classical Dynamics
7.4 Case Studies of Non-adiabatic Photochemistry
7.4.1 MCTDH Study of the Homolysis of the O–O Bond in Anthracene-9,10-endoperoxide
7.4.2 DD-vMCG Study of the Photoisomerisation of a Cyanine Model
7.4.3 TSH Study of the Photoactivation of the Photoactive Yellow Protein
7.5 Conclusions
References
8 The Interplay of Nuclear and Electron Wavepacket Motion in the Control of Molecular Processes: A Theoretical Perspective
8.1 Introduction
8.2 Concepts of Coherent Control for Molecular Motion
8.2.1 Theory for Single Parameter Control
8.2.2 Single Parameter Control
8.2.3 Multiparameter Control: OCT
8.2.4 Coherent Control in the Sub-femtosecond Domain: Theory for Coupled Electron Nuclear Motion
8.3 Molecular Control Including the Electron Motion Implicitly and Explicitly
8.3.1 Photoreactions Mediated via Conical Intersections
8.3.2 Control of Electron Motion in Diatomics
8.3.2.1 CEP Control
8.3.2.2 Strong Field Temporal Control
8.4 What Can Be Learned for Larger Molecules?
References
9 The Dynamics of Quantum Computing in Molecules
9.1 The Advent of Quantum Computing
9.1.1 Qubits, Quantum Gates and Quantum Algorithms
9.1.2 Global Phase Alignment
9.1.3 Quantum Superpositions and Quantum Parallelism
9.1.4 Advantages of a Quantum Computer
9.1.5 Universal Quantum Computer and Quantum Simulator
9.1.6 Experimentally Realized and Proposed Quantum Computer Architectures
9.2 Procedure for Performing a Quantum Computation
9.2.1 System Preparation: Qubit Initialization
9.2.2 System Manipulation: Apply Quantum Algorithms
9.2.3 System Readout: Determine the Solution
9.3 Molecular Quantum Computing Using Shaped Laser Pulses
9.3.1 Quantum Dynamics: Laser/Molecule Interaction
9.3.2 Optimal Control Theory (OCT)
9.3.3 Genetic Algorithm (GA) Optimization
9.3.3.1 Laser Field
9.3.3.2 Fidelity and Average Population
9.4 Summary and Future Directions
References
10 Conclusions
References
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