Reviews in Computational Chemistry, Volume 23

ISBN-13: 9780470082010 / Angielski / Twarda / 2007 / 484 str.

Kenny B. Lipkowitz; Thomas R. Cundari; Donald B. Boyd

Opis

THIS VOLUME, LIKE THOSE PRIOR TO IT, FEATURES CHAPTERS BY EXPERTS IN VARIOUS FIELDS OF COMPUTATIONAL CHEMISTRY. Volume 23 COVERS LINEAR SCALING METHODS FOR QUANTUM CHEMISTRY, VARIATIONAL TRANSITION STATE THEORY, COARSE GRAIN MODELING OF POLYMERS, SUPPORT VECTOR MACHINES, CONICAL INTERSECTIONS, ANALYSIS OF INFORMATION CONTENT USING SHANNON ENTROPY, AND HISTORICAL INSIGHTS INTO HOW COMPUTING EVOLVED IN THE PHARMACEUTICAL INDUSTRY. FROM REVIEWS OF THE SERIES "Reviews in Computational Chemistry remains the most valuable reference to methods and techniques in computational chemistry."
--JOURNAL OF MOLECULAR GRAPHICS AND MODELLING "One cannot generally do better than to try to find an appropriate article in the highly successful Reviews in Computational Chemistry. The basic philosophy of the editors seems to be to help the authors produce chapters that are complete, accurate, clear, and accessible to experimentalists (in particular) and other nonspecialists (in general)."
--JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

Recenzje

"...another gem in the...series...a must for any library as well as for the leading labs in the world." ( Journal of the American Chemical Society, August 22, 2007)

Spis treści

1. Linear–Scaling Methods in Quantum Chemistry (Christian Ochsenfeld, Jörg Kussmann, and Daniel S. Lambrecht).

Introduction.

Some Basics of SCF Theory.

Direct SCF Methods and Two–Electron Integral Screening.

Schwarz Integral Estimates.

Multipole–Based Integral Estimates (MBIE).

Calculation of Integrals via Multipole Expansion.

A First Example.

Derivation of the Multipole Expansion.

The Fast Multipole Method: Breaking the Quadratic Wall.

Fast Multipole Methods for Continuous Charge Distributions.

Other Approaches.

Exchange–Type Contractions.

The Exchange–Correlation Matrix of KS–DFT.

Avoiding the Diagonalization Step Density Matrix–Based SCF.

General Remarks.

Tensor Formalism.

Properties of the One–Particle Density Matrix.

Density Matrix–Based Energy Functional.

Curvy Steps in Energy Minimization.

Density Matrix–Based Quadratically Convergent SCF (D–QCSCF).

Implications for Linear–Scaling Calculation of SCF Energies.

SCF Energy Gradients.

Molecular Response Properties at the SCF Level.

Vibrational Frequencies.

NMR Chemical Shieldings.

Density Matrix–Based Coupled Perturbed SCF (D–CPSCF).

Outlook on Electron Correlation Methods for Large Systems.

Long–Range Behavior of Correlation Effects.

Rigorous Selection of Transformed Products via Multipole–Based Integral Estimates (MBIE).

Implications.

Conclusions.

References.

2. Conical Intersections in Molecular Systems (Spiridoula Matsika).

Introduction.

General Theory.

The Born Oppenheimer Approximation and its Breakdown: Nonadiabatic Processes.

Adiabatic–Diabatic Representation.

The Noncrossing Rule.

The Geometric Phase Effect.

Conical Intersections and Symmetry.

The Branching Plane.

Characterizing Conical Intersections: Topography.

Derivative Coupling.

Electronic Structure Methods for Excited States.

Multiconfiguration Self–Consistent Field (MCSCF).

Multireference Configuration Interaction (MRCI).

Complete Active Space Second–Order Perturbation Theory (CASPT2).

Single Reference Methods.

Choosing Electronic Structure Methods for Conical Intersections.

Locating Conical Intersections.

Dynamics.

Applications.

Conical Intersections in Biologically Relevant Systems.

Beyond the Double Cone.

Three–State Conical Intersections.

Spin–Orbit Coupling and Conical Intersections.

Conclusions and Future Directions.

Acknowledgments.

References.

3. Variational Transition State Theory with Multidimensional Tunneling (Antonio Fernandez–Ramos, Benjamin A. Ellingson, Bruce C. Garrett, and Donald G. Truhlar).

Introduction.

Variational Transition State Theory for Gas–Phase Reactions.

Conventional Transition State Theory.

Canonical Variational Transition State Theory.

Other Variational Transition State Theories.

Quantum Effects on the Reaction Coordinate.

Practical Methods for Quantized VTST Calculations.

The Reaction Path.

Evaluation of Partition Functions.

Harmonic and Anharmonic Vibrational Energy Levels.

Calculations of Generalized Transition State Number of States.

Quantum Effects on Reaction Coordinate Motion.

Multidimensional Tunneling Corrections Based on the Adiabatic Approximation.

Large Curvature Transmission Coefficient.

The Microcanonically Optimized Transmission Coefficient.

Building the PES from Electronic Structure Calculation.

Direct Dynamics with Specific Reaction Parameters.

Interpolated VTST.

Dual–Level Dynamics.

Reactions in Liquids.

Ensemble–Averaged Variational Transition State Theory.

Gas–Phase Example: H +CH₄.

Liquid–Phase Example: Menshutkin Reaction.

Concluding Remarks.

Acknowledgments.

References.

4. Coarse–Grain Modeling of Polymers (Roland Faller).

Introduction.

Defining the System.

Choice of Model.

Interaction Sites on the Coarse–Grained Scale.

Static Mapping.

Single–Chain Distribution Potentials.

Simplex.

Iterative Structural Coarse–Graining.

Mapping Onto Simple Models.

Dynamic Mapping.

Mapping by Chain Diffusion.

Mapping through Local Correlation Times.

Direct Mapping of the Lennard–Jones Time.

Coarse–Grained Monte Carlo Simulations.

Reverse Mapping.

A Look Beyond Polymers.

Conclusions.

Acknowledgments.

References.

5. Analysis of Chemical Information Content Using Shannon Entropy (Jeffrey W. Godden and JÜrgen Bajorath).

Introduction.

Shannon Entropy Concept.

Descriptor Comparison.

Influence of Boundary Effects.

Extension of SE Analysis for Profiling of Chemical Libraries.

Information Content of Organic Molecules.

Shannon Entropy in Quantum Mechanics, Molecular Dynamics, and Modeling.

Examples of SE and DSE Analysis.

Conclusions.

References.

6. Applications of Support Vector Machines in Chemistry (Ovidiu Ivanciuc).

Introduction.

A Nonmathematical Introduction to SVM.

Pattern Classification.

The Vapnik Chervonenkis Dimension.

Pattern Classification with Linear Support Vector Machines.

SVM Classification for Linearly Separable Data.

Linear SVM for the Classification of Linearly Non–Separable Data.

Nonlinear Support Vector Machines.

Mapping Patterns to a Feature Space.

Feature Functions and Kernels.

Kernel Functions for SVM.

Hard Margin Nonlinear SVM Classification.

Soft Margin Nonlinear SVM Classification.

n–SVM Classification.

Weighted SVM for Imbalanced Classification.

Multi–class SVM Classification.

SVM Regression.

Optimizing the SVM Model.

Descriptor Selection.

Support Vectors Selection.

Jury SVM.

Kernels for Biosequences.

Kernels for Molecular Structures.

Practical Aspects of SVM Classification.

Predicting the Mechanism of Action for Polar and Nonpolar Narcotic Compounds.

Predicting the Mechanism of Action for Narcotic and Reactive Compounds.

Predicting the Mechanism of Action from Hydrophobicity and Experimental Toxicity.

Classifying the Carcinogenic Activity of Polycyclic Aromatic Hydrocarbons.

Structure–Odor Relationships for Pyrazines.

Practical Aspects of SVM Regression.

SVM Regression QSAR for the Phenol Toxicity to Tetrahymena pyriformis.

SVM Regression QSAR for Benzodiazepine Receptor Ligands.

SVM Regression QSAR for the Toxicity of Aromatic Compounds to Chlorella vulgaris.

SVM Regression QSAR for Bioconcentration Factors.

Review of SVM Applications in Chemistry.

Recognition of Chemical Classes and Drug Design.

QSAR.

Genotoxicity of Chemical Compounds.

Chemometrics.

Sensors.

Chemical Engineering.

Text Mining for Scientific Information.

SVM Resources on the Web.

SVM Software.

Conclusions.

References.

7. How Computational Chemistry Became Important in the Pharmaceutical Industry (Donald B. Boyd).

Introduction.

Germination: The 1960s.

Gaining a Foothold: The 1970s.

Growth: The 1980s.

Gems Discovered: The 1990s.

Final Observations.

Acknowledgments.

References.

Author Index.

Subject Index.

O autorze

Kenny B. Lipkowitz is a recently retired Professor of Chemistry from North Dakota State University.

Tom Cundari is Professor of Chemistry at the University of North Texas.