Modern Methods and Algorithms of Quantum Chemistry

Transcription

1 John von Neumann Institute for Computing (NIC) r "* UNiVERsrr. INFORMATION'^?;ij;'ioTHEK Johannes Grotendorst (Editor) Modern Methods and Algorithms of Quantum Chemistry Winterschool, February 2000 Forschungszentrum Julich, Germany Proceedings, Second Edition organized by John von Neumann Institute for Computing in cooperation with Arbeitsgemeinschaft fur Theoretische Chemie NIC Series Volume 3 ISBN

2 CONTENTS Industrial Challenges for Quantum Chemistry Ansgar Schafer 1 1 Introduction 1 2 Application Fields of Quantum Chemistry in Industry 2 3 Unsolved Problems 3 4 Conclusion 5 Ab Initio Treatment of Large Molecules Reinhari Ahlrichs, Simon Elliott, and Uwe Huniar 7 1 Introduction 7 2 The Zoo of Methods 8 3 Computer Hardware: Another Zoo 14 4 Calculating some Large Systems 16 5 Outlook 23 Parallel Programming Models, Tools and Performance Analysis Michael Gerndt 27 1 Introduction 27 2 Programming Models 30 3 Parallel Debugging 36 4 Performance Analysis 36 5 Summary 43 Basic Numerical Libraries for Parallel Systems Inge Gutheil 47 1 Introduction 47 2 Data Distributions 48 3 User-Interfaces 51 4 Performance 54 5 Conclusions 62 Tools for Parallel Quantum Chemistry Software Thomas Steinke 67 1 Introduction 67 2 Basic Tasks in Typical Quantum Chemical Calculations 68 3 Parallel Tools in Today's Production Codes 70 4 The TCGMSG Library 71 5 The Global Array Toolkit 72 6 The Distributed Data Interface Used in GAMESS (US) 82 7 Further Reading 85 8 Summary 85

3 Ab Initio Methods for Electron Correlation in Molecules Peter Knowles, Martin Schu'tz, and Hans-Joachim Werner 97 1 Introduction 97 2 Closed-Shell Single-Reference Methods Open-Shell Single-Reference Methods Linear Scaling Local Correlation Methods Multireference Electron Correlation Methods Integral-Direct Methods 161 R12 Methods, Gaussian Geminals Wim Klopper Introduction Errors in Electronic-Structure Calculations The Basis-Set Error Coulomb Hole Many-Electron Systems Second Quantization Explicitly Correlated Coupled-Cluster Doubles Model Weak Orthogonality Techniques R12 Methods Explicitly Correlated Gaussians Similarity Transformed Hamiltonians MP2-Limit Corrections Computational Aspects of R12 Methods Numerical Examples Concluding Remark 219 Direct Solvers for Symmetric Eigenvalue Problems Bruno Lang Setting the Stage Eigenvalue Computations: How Good, How Fast, and How? Tools of the Trade: Basic Orthogonal Transformations Phase I: Reduction to Tridiagonal Form Phase II: Methods for Tridiagonal Matrices Methods without Initial Tridiagonalization Synopsis Available Software 256 Semiempirical Methods Walter Thiel Introduction Established Methods Beyond the MNDO Model: Orthogonalization Corrections NMR Chemical Shifts 269 n

4 5 Analytic Derivatives Parallelization Linear Scaling and Combined QM/MM Approaches Conclusions 280 Hybrid Quantum Mechanics/Molecular Mechanics Approaches Paul Sherwood Introduction Terminology Overview of QM/MM Schemes The Issue of Conformational Complexity Software Implementation Summary and Outlook 299 Subspace Methods for Sparse Eigenvalue Problems Bernhard Steffen Introduction Eigenvalue Extraction Update Procedures Problems of Implementation and Parallelization Conclusions 313 Computing Derivatives of Computer Programs Christian Bischof and Martin Biicker Introduction Basic Modes of Automatic Differentiation Design of Automatic Differentiation Tools Using Automatic Differentiation Tools Concluding Remarks 325 Ab Initio Molecular Dynamics: Theory and Implementation Dominik Marx and Jurg Hutter Setting the Stage: Why Ab Initio Molecular Dynamics? Basic Techniques: Theory Basic Techniques: Implementation within the CPMD Code Advanced Techniques: Beyond Applications: From Materials Science to Biochemistry 446 in

5 Relativistic Electronic-Structure Calculations for Atoms and Molecules Markus Reiher and Bernd Hefi Qualitative Description of Relativistic Effects Fundamentals of Relativistic Quantum Chemistry Numerical 4-Component Calculations for Atoms Molecular Calculations Epilogue 500 Effective Core Potentials Michael Dolg Introduction All-Electron Hamiltonian Valence-Only Hamiltonian Analytical Form of Pseudopotentials Adjustment of Pseudopotentials Core Polarization Potentials Calibration Studies A Few Hints for Practical Calculations 532 Molecular Properties Jiirgen Gauss Introduction Molecular Properties as Analytical Derivatives Magnetic Properties Frequency-Dependent Properties Summary 585 Tensors in Electronic Structure Theory: Basic Concepts and Applications to Electron Correlation Models Martin Head-Gordon, Michael Lee, Paul Maslen, Troy van Voorhis, and Steven Gwaltney Introduction Basic Tensor Concepts Many-Electron Theory Nonorthogonal Functions for Local Electron Correlation An Overview of Other Applications Conclusions 635 IV