COMPUTATIONAL METHODS FOR LARGE SYSTEMS -- Contents -- Contributors -- Preface: Choosing the Right Method for Your Problem -- A DFT: THE BASIC WORKHORSE -- 1 Principles of Density Functional Theory: Equilibrium and Nonequilibrium Applications -- 1.1 Equilibrium Theories -- 1.2 Local Approximations -- 1.3 Kohn-Sham Formulation -- 1.4 Why DFT Is So Successful -- 1.5 Exact Properties of DFTs -- 1.6 Time-Dependent DFT -- 1.7 TDDFT and Transport Calculations -- 1.8 Modeling Reservoirs In and Out of Equilibrium -- 2 SIESTA: A Linear-Scaling Method for Density Functional Calculations -- 2.1 Introduction -- 2.2 Methodology -- 2.3 Future Perspectives -- 3 Large-Scale Plane-Wave-Based Density Functional Theory: Formalism, Parallelization, and Applications -- 3.1 Introduction -- 3.2 Plane-Wave Basis Set -- 3.3 Pseudopotential Plane-Wave Method -- 3.4 Charged Systems -- 3.5 Exact Exchange -- 3.6 Wavefunction Optimization for Plane-Wave Methods -- 3.7 Car-Parrinello Molecular Dynamics -- 3.8 Parallelization -- 3.9 AIMD Simulations of Highly Charged Ions in Solution -- 3.10 Conclusions -- B HIGHER-ACCURACY METHODS -- 4 Quantum Monte Carlo, Or, Solving the Many-Particle Schrödinger Equation Accurately While Retaining Favorable Scaling with System Size -- 4.1 Introduction -- 4.2 Variational Monte Carlo -- 4.3 Wavefunctions and Their Optimization -- 4.4 Diffusion Monte Carlo -- 4.5 Bits and Pieces -- 4.6 Applications -- 4.7 Conclusions -- 5 Coupled-Cluster Calculations for Large Molecular and Extended Systems -- 5.1 Introduction -- 5.2 Theory -- 5.3 General Structure of Parallel Coupled-Cluster Codes -- 5.4 Large-Scale Coupled-Cluster Calculations -- 5.5 Conclusions -- 6 Strongly Correlated Electrons: Renormalized Band Structure Theory and Quantum Chemical Methods -- 6.1 Introduction -- 6.2 Measure of the Strength of Electron Correlations.

6.3 Renormalized Band Structure Theory -- 6.4 Quantum Chemical Methods -- 6.5 Conclusions -- C MORE-ECONOMICAL METHODS -- 7 The Energy-Based Fragmentation Approach for Ab Initio Calculations of Large Systems -- 7.1 Introduction -- 7.2 The Energy-Based Fragmentation Approach and Its Generalized Version -- 7.3 Results and Discussion -- 7.4 Conclusions -- 7.5 Appendix: Illustrative Example of the GEBF Procedure -- 8 MNDO-like Semiempirical Molecular Orbital Theory and Its Application to Large Systems -- 8.1 Basic Theory -- 8.2 Parameterization -- 8.3 Natural History or Evolution of MNDO-like Methods -- 8.4 Large Systems -- 9 Self-Consistent-Charge Density Functional Tight-Binding Method: An Efficient Approximation of Density Functional Theory -- 9.1 Introduction -- 9.2 Theory -- 9.3 Performance of Standard SCC-DFTB -- 9.4 Extensions of Standard SCC-DFTB -- 9.5 Conclusions -- 10 Introduction to Effective Low-Energy Hamiltonians in Condensed Matter Physics and Chemistry -- 10.1 Brief Introduction to Second Quantization Notation -- 10.2 Hückel or Tight-Binding Model -- 10.3 Hubbard Model -- 10.4 Heisenberg Model -- 10.5 Other Effective Low-Energy Hamiltonians for Correlated Electrons -- 10.6 Holstein Model -- 10.7 Effective Hamiltonian or Semiempirical Model? -- D ADVANCED APPLICATIONS -- 11 SIESTA: Properties and Applications -- 11.1 Ethynylbenzene Adsorption on Au(111) -- 11.2 Dimerization of Thiols on Au(111) -- 11.3 Molecular Dynamics of Nanoparticles -- 11.4 Applications to Large Numbers of Atoms -- 12 Modeling Photobiology Using Quantum Mechanics and Quantum Mechanics/Molecular Mechanics Calculations -- 12.1 Introduction -- 12.2 Computational Strategies: Methods and Models -- 12.3 Applications -- 12.4 Conclusions -- 13 Computational Methods for Modeling Free-Radical Polymerization -- 13.1 Introduction.

13.2 Model Reactions for Free-Radical Polymerization Kinetics -- 13.3 Electronic Structure Methods -- 13.4 Calculation of Kinetics and Thermodynamics -- 13.5 Conclusions -- 14 Evaluation of Nonlinear Optical Properties of Large Conjugated Molecular Systems by Long-Range-Corrected Density Functional Theory -- 14.1 Introduction -- 14.2 Nonlinear Optical Response Theory -- 14.3 Long-Range-Corrected Density Functional Theory -- 14.4 Evaluation of Hyperpolarizability for Long Conjugated Systems -- 14.5 Conclusions -- 15 Calculating the Raman and HyperRaman Spectra of Large Molecules and Molecules Interacting with Nanoparticles -- 15.1 Introduction -- 15.2 Displacement of Coordinates Along Normal Modes -- 15.3 Calculation of Polarizabilities Using TDDFT -- 15.4 Derivatives of the Polarizabilities with Respect to Normal Modes -- 15.5 Orientation Averaging -- 15.6 Differential Cross Sections -- 15.7 Surface-Enhanced Raman and HyperRaman Spectra -- 15.8 Application of Tensor Rotations to Raman Spectra for Specific Surface Orientations -- 15.9 Resonance Raman -- 15.10 Determination of Resonant Wavelength -- 15.11 Summary -- 16 Metal Surfaces and Interfaces: Properties from Density Functional Theory -- 16.1 Background, Goals, and Outline -- 16.2 Methodology -- 16.3 Structure and Properties of Iron Surfaces -- 16.4 Structure and Properties of Iron Interfaces -- 16.5 Summary, Conclusions, and Future Work -- 17 Surface Chemistry and Catalysis from Ab Initio-Based Multiscale Approaches -- 17.1 Introduction -- 17.2 Predicting Surface Structures and Phase Transitions -- 17.3 Surface Phase Diagrams from Ab Initio Atomistic Thermodynamics -- 17.4 Catalysis and Diffusion from Ab Initio Kinetic Monte Carlo Simulations -- 17.5 Summary -- 18 Molecular Spintronics -- 18.1 Introduction -- 18.2 Theoretical Background -- 18.3 Numerical Implementation -- 18.4 Examples.

18.5 Conclusions -- 19 Calculating Molecular Conductance -- 19.1 Introduction -- 19.2 Outline of the NEGF Approach -- 19.3 Electronic Structure Challenges -- 19.4 Chemical Trends -- 19.5 Features of Electronic Transport -- 19.6 Applications -- 19.7 Conclusions -- Index.