Exploring Chemistry with Electronic Structure Methods Second Edition James B. Foresman and Aleen FrischTl Exploring Chemistry with Electronic Structure Methods Second Edition _James B. Foresman #leen Frisch G Gaussian, Tic. ~~ Pittsburgh, PA‘The information contained in this publication is believed to be accurate and reliable. However, Gaussian, Inc. makes no representation of warranties with respect to this document or the software described herein. That software is distributed only in accond with a writen license. Gaussian, Inc. disclaims any implied warranties of merchantability ‘or fitness of this document for any purpose. Information in this document is subject to change without notice and does not represent a commitment on the part of Gaussian, Ine No part ofthis document may be reproduced or transmitted in any form orby any means, slectronic or mechanical, including photocopying, for any purpose without the express fen consent of Gaussian, In. Copyright © 1993, 1995.96, Gaussian, Inc. A Rights Reserved Gaussian, Gaussian 90, Gaussian 92, Gaussian 94 and Gaussian 94W are registered trademarks of Gaussian, Inc. All other trademarks and registered trademarks are the properties of their respective holders. For more information about the Gaussian program, contac: Gaussian, Inc Camegie Office Park, Building 6 Pittsburgh, PA 15106US.A, oie: 412-279-6700 fax 812-279-2118 ‘email: info@gaussian.com Colophon: ‘This book was created on a Gateway 2000 486-based computer using FrameMaker, FreeHand, ChemDraw, Photoshop and PreezeFrame. Body tet is set in $/11 Minion; headings and captions are set in Futura ISBN 0-9636769-3-8 Printing History: Corresponds to: April 1993 First Edition. Gaussian 92 Revision D.1 and higher. March 1994 Second Printing, ‘August 1996 Second Edition. Gaussian 94 Revision D.2 end higher. Printed in the US.A.Quick Topic Finder ‘Accuracies of Model Chemistries 146, 157 Atomic Charges eon a 194 CASSCF Method son 28 ‘Complete Basis Set Methods 154 Density Functional TREOYY ws . us Excited States 213 Frequency Calculations. : ea G2Caulations sn eaaee 150 ‘Hyperfine Coupling Constants . 136 IRC Calculations — “73 Inodesmie Reactions = 181 Methods ‘Accuracies Compared usnsnssnns snus 16, 157 Relative Costs pease z Model Chemistries ‘Selection Recommendations seen 96 Molecular Orbital 18 NMR Properties socnnnnnne 21, $3, 104 ‘Optimizations Performing somes : 2 ‘Advanced Techniques... ~ a (Characterizing Stationary Points vo 70 Locating Transition Structures . vn AB Potential Energy Surface Scans 2 m7 Reaction Path Following 173) Resource Requirements 12 Seale Factors for Frequencies/2PEs 64 SN2 Reactions ss ns vn 208 Solvent Effects 237 Stability Calculations : 4 ‘Thermochemistry. ve a 66, 141 “Transition Structure Optimizations. 46 sploring Chemisty with Eeromie Structure Methods itList of Examples and Exercises... Table of Input Fils. List of “To the Teacher” Boxes. Acknowledgments... Preface: About This Work. ‘Who Should Read This Book? ‘Overview and Goals. Examples and Exercise. Organizational Structure... Where to Get Additional Information, ‘Typographic and Graphical Conventions. Quick Start: Running Gaussian ‘Tutorial for UNIX and VMS Systems.. Converting a Structure from a Graphics Program. Batch Processing... Tutorial for Windows Systems Converting a Structure from a Graphics Program. Drag-and-Drop Execution, A Quick Tour of Gaussian Output, Part 1: Essential Concepts & Techniques ‘Chapter 1: Computational Models & Model Chemistries. ‘An Overview of Computational Chemistry. Molecular Mechanics Electronic Structure Methods. Model Chemists Defining Model Chemistries References Exploring Chemistry with lectronic Structure MethodsTabi of Contents Chapter 2: Single Point Energy Calculations 8 Setting Up Energy Calculations cel The Rowte SCHON sn sn 4 The Title Section vo 5 The Molecule Specification Section en. ol Maltistep Jobs snl Locating Results in Gaussian! OUtpU veer 16 Standard Orientation Geometry. . “16 Energy. ve Molecular Orbitas and Orbital Energies nse 18 Charge Distib tio ee 20 Dipole and Higher Mulipole Moments. 20 CBU Time and Other Resource Us9g@ nmnrnnnnnnnn 2 Predicting NMR Properties. : ee Exercises — ss 2 References = 7 Chapter 3: Geometry Opti : 39 Potential Energy Surfaces — se 39 Locating Minima. sn cn Convergence Criteria wl Preparing Input for Geometry Optimizations sn 82 Examining Optimization Output. sn 3 Locating Transition Structures ve 46 Handling Difficult Optimization Cases n..- a7 Exercises — sn ” References. 59 Chapter 4: Frequency Calculations soe 6 Predicting IR and Raman Speetf2 ess se Input for Frequency Jobs. 62 Frequencies and Intensities. 63 Normal Modes 8 Thermochemistry... 66 Zero-Point Energy and Thermal Energy 68 Polarizability and Hyperpolarizability. « Characterizing Stationary Point... vo 70 EXCIC8€8 cere so 16 References — 90 vi Exploring Chemis with Electronic Structure MethodsTable of Content Part 2: Model Chemistries Introduction 93 Model Chemists. 93 Terminology... 98 Recommendations for Selecting Research Models %6 Chapter 5: Bass Set Effects... 7 Minimal Bass Sets 7 Split Valence Basis Sts °8 Polarized Basis ets... 8 Diffuse Functions... 99 igh Angular Momentum Basis Sets. 100 Basis Sets for Post-Third-Row Atoms 101 Exercises 103, References 110 Chapter 6 Selecting an Appropriate Theoretical Method. ut Using Semi-Empirical Methods ut Limitations of Semi-Empirical Methods 13 Electron Correlation and Post-SCF Methods 14 The Limits of Hartree-Fock Theory. 115 ‘The MPn Methods, 116 Coupled Cluster and Quadratic Configuration Interaction Methods.117 Density Functional Theory Methods. 118 Resource Usage 12 Exercises wl References 19 ‘Chapter 7: High Accuracy Energy Models. ut Predicting Thermochemistry. ut ‘Atomization Energies. coll Electron ATfinitie nn 142 Ionization Potentials. 13 Proton Affinities 3 Evaluating Model Chemistries. 7 “The G2 Molecile Set (and Pitfalls in Is Interpretation) 44 Relative Accuracis of Selected Model Chemistries 146 . wiry with lero Stacure Methods vilTable of Contents Compound Method. 150 Gaussan-1 and Gavssian-2 Theories 130 Complete Bass Set Methods ase sercises , a) References 60 Part 3: Applications Chapter: Studying Chemical Reactions and Reactivity. 16s Interpreting the Electron Density. 16S ‘Computing Enthalpies of Reaction.. so 166, Studying Potential Energy Surfaces... 169 Potential Energy Surface SCAMS onsen vt Reaction Path Following... 173 Running IRC Caleulations.. 173 Exploring a Potential Energy Surface... 175 Molecular Dissociation of Formaldehyde... 75 ‘The 1,2 Hydrogen Shift Reaction sev. eeeeesemieet 70 A Final Note on IRC Caleulations... ea Isodesmic Reactions, sw 181 Limitations of Isodesmic Rea su B3 Exercises. 18S References... 201 Chapter 9: Modeling Excited States ....mmu eee 13) Running Excited State Calculations. 213 Ch-Singles Output eon eee 215 Excited State Optimizations and Frequencies... 216 Exercises 218 References 3S Chapter 10: Modeling Systems in Solution. 237 Reaction Field Models of Solvation... 237 Limitations of the Onsager Model... 238 Running SCRF Calculations., oan 10239 Molecular Volume Calculations. eee 0) Locating Results in Gaussiat OULPUE oecsnnrne 240 EXEL Ci8€5 cnn : : DAD References 248 vill Eqlorng Chemis with Electronic Structure Methods‘Table of Contents Appendices Appendix A: The Theoretical Background, ‘The Schrodinger Equation ‘The Molecular Hamiltonian... Atomic Units... ‘The Born-Oppenheimer Approximation Restrictions on the Wavefunction. Hartree-Fock Theory, Molecular Orbitals... The Roothaan-Hall Equations Open Shell Methods... Electron Correlation Methods. Configuration Interaction Moller-Plesset Perturbation Theory. Density Functional Theory... ‘The Complete Basis Set Extrapolation. References Appendix B: Overview of Gaussian Input... Input File Sections. sn ‘The Route Section.. More Complex Z-Matrices . Using Variables in a Z-matrix. Mullti-Step Jobs. Index. eee ses IT Physical Constants & Conversion Factors Exploring Chemistry with EleconicSuctue Methods ix