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NBO 7.0 Program Manual Natural Bond Orbital Analysis

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NBO 7.0 Program Manual Natural Bond Orbital Analysis NBO 7.0 Program Manual Natural Bond Orbital Analysis Programs compiled and edited by Frank Weinhold and Eric D. Glendening F. Weinhold: Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706 E-mail: [email protected] Phone: (608)262-0263 E. D. Glendening: Department of Chemistry and Physics, Indiana State University, Terre Haute, Indiana 47809 E-mail: [email protected] Phone: (812)237-2235 NBO7 Website: http://nbo7.chem.wisc.edu/ (c) Copyright 1996-2021 Board of Regents of the University of Wisconsin System on behalf of the Theoretical Chemistry Institute. All Rights Reserved. Table of Contents Table of Contents i Preface: HOW TO USE THIS MANUAL iv Table 1: NBO Keyword/Keylist Quick Summary v A. GETTING STARTED A.1 INTRODUCTION TO THE NBO 7.0 PROGRAM A-1 A.1.1 What Does the NBO Program Do? A-1 A.1.2 Input and Output A-4 A.1.3 General Capabilities and Restrictions A-6 A.1.4 References and Relationship to Previous Versions A-7 A.1.5 What's New in NBO 7.0? A-10 A.2 INSTALLING THE NBO PROGRAM A-14 A.3 TUTORIAL EXAMPLE FOR METHYLAMINE A-16 A.3.1 Running the Example A-16 A.3.2 Natural Population Analysis A-18 A.3.3 Natural Bond Orbital Analysis A-21 A.3.4 NHO Directional Analysis A-25 A.3.5 Perturbation Theory Energy Analysis A-26 A.3.6 NBO Summary A-27 B. NBO USER'S GUIDE B.1 INTRODUCTION TO THE NBO USER'S GUIDE AND NBO KEYLISTS B-1 B.2 THE $NBO KEYLIST B-3 B.2.1 Overview of $NBO Keywords B-3 B.2.2 Job Control Keywords B-5 B.2.3 Job Threshold Keywords B-7 B.2.4 Matrix Output Keywords B-9 B.2.5 Other Output Control Keywords B-14 B.2.6 Print Level Keywords B-15 B.2.7 Semi-Documented Additional Keywords B-16 B.3 THE $CORE LIST B-18 B.4 THE $CHOOSE KEYLIST (DIRECTED NBO SEARCH) B-20 B.5 THE $DEL KEYLIST (NBO ENERGETIC ANALYSIS) B-23 B.5.1 Introduction to NBO Energetic Analysis B-23 B.5.2 The Nine Deletion Types B-25 B.5.3 Input for UHF Analysis B-29 B.6 NBO ILLUSTRATIONS B-31 B.6.1 Introduction B-31 B.6.2 NLMO Keyword B-32 B.6.3 DIPOLE Keyword B-34 B.6.4 Matrix Output Keywords B-36 B.6.5 BNDIDX Keyword B-39 B.6.6 Strong Delocalization: Benzene B-42 B.6.7 NOBOND Keyword: Hydrogen Fluoride B-46 i B.6.8 Hypovalent Bonding: Diborane B-49 B.6.9 NBO Directed Search ($CHOOSE Keylist) B-53 B.6.10 NBO Energetic Analysis ($DEL Keylist) B-56 B.6.11 Open-Shell UHF Output: Methyl Radical B-59 B.6.12 Effective Core Potential: Cu2 Dimer B-63 B.7 FILE47: INPUT FOR THE GenNBO STAND-ALONE NBO PROGRAM B-68 B.7.1 Introduction B-68 B.7.2 Format of FILE47 B-69 B.7.3 $GENNBO Keylist B-71 B.7.4 $COORD Keylist B-73 B.7.5 $BASIS Datalist B-74 B.7.6 $CONTRACT Datalist B-76 B.7.7 $WF Datalist B-78 B.7.7 Matrix Datalists B-80 B.8 NRT: NATURAL RESONANCE THEORY ANALYSIS B-82 B.8.1 Introduction: Single and Multi-Reference NRT Analysis B-82 B.8.2 NRT Job Control Keywords B-86 B.8.3 Auxiliary $NRTSTR Keylist Input B-89 B.8.4 NRT Illustrations B-91 B.9 NBBP: NATURAL BOND-BOND POLARIZABILITY INDICES B-102 B.9.1 Introduction to NBBP B-102 B.9.2 NBBP Keyword Usage and Sample Output B-103 B.10 STERIC: NATURAL STERIC ANALYSIS B-106 B.10.1 Introduction to Natural Steric Analysis B-106 B.10.2 STERIC Keyword Usage and Sample Output B-108 B.11 NEDA: NATURAL ENERGY DECOMPOSITION ANALYSIS B-111 B.11.1 Introduction to NEDA B-111 B.11.2 Performing NEDA B-113 B.11.3 Sample NEDA Input B-117 B.11.4 Sample NEDA Output B-122 B.12 CHECKPOINTING OPTIONS B-135 B.12.1 Introduction B-135 B.12.2 Checkpointing Options B-136 B.12.3 Checkpoint Permutation Lists B-139 B.12.4 Example: CAS/NBO and CI/NBO Calculations B-141 B.13 CMO: CANONICAL MO ANALYSIS B-142 B.13.1 Introduction B-142 B.13.2 CMO Keyword Usage and Sample Output B-143 B.14 NCS: NATURAL CHEMICAL SHIELDING ANALYSIS B-146 B.14.1 Introduction to Natural Chemical Shielding Analysis B-146 B.14.2 NCS Keyword Usage B-149 B.14.3 NCS Sample Output B-152 B.15 NJC: NATURAL J-COUPLING ANALYSIS B-155 B.15.1 Introduction to Natural J-Coupling Analysis B-155 B.15.2 NJC Keyword Usage and Sample Input B-161 B.15.3 NJC Sample Output B-163 ii B.16 3-CENTER, 4-ELECTRON HYPERBOND SEARCH B-166 B.16.1 Introduction B-166 B.16.2 Sample Output B-168 B.17 NBCP: NATURAL BOND CRITICAL POINT ANALYSIS B-170 B.17.1 Introduction to Natural Bond Critical Point Analysis B-170 B.17.2 NBCP Keyword Usage B-173 B.17.3 Additional NBCP_BP and NBCP_PT Keyword Options B-175 B.17.4 NBCP Sample Output B-176 B.18 NCE: NATURAL COULOMB ELECTROSTATICS ANALYSIS B-181 B.18.1 Introduction B-181 B.18.2 NCE Keyword Usage and Sample Output B-183 B.19 NCU: NATURAL CLUSTER UNIT ANALYSIS B-185 B.19.1 Introduction to NCU Analysis B-185 B.19.2 NCU Sample Output B-187 B.20 PROP: GENERAL 1E PROPERTY ANALYSIS B-189 B.21 MATRIX: GENERAL MATRIX OPERATOR AND B-192 TRANSFORMATION OUTPUT B.22 STRUCTURAL AND GRAPHICAL OUTPUT KEYWORDS B-195 B.23 EFFECTIVELY UNPAIRED ELECTRON DISTRIBUTION B-199 B.24 NPEPA: NATURAL POLYELECTRON POPULATION ANALYSIS B-205 B.24.1 Introduction to NPEPA B-205 B.24.2 NPEPA Keywords and the $NPEPA Keylist B-207 B.24.3 Sample Input and Output B-211 B.25 RDM2: 2ND-ORDER REDUCED DENSITY MATRIX ELEMENTS B-215 B.25.1 Introduction B-215 B.25.2 RDM2 Keyword and Sample Output B-218 B.26 RNBO: RESONANCE NATURAL BOND ORBITALS B-220 B.26.1 Introduction B-220 B.26.2 RNBO and PRNBO Keywords B-222 B.26.3 RNBO Output B-223 iii PREFACE: HOW TO USE THIS MANUAL The NBO7 Manual consists of two major divisions: Section A (“Getting Started”) contains introductory and one-time information for the novice user – what the program does, new program functionality, program installation, and a brief tutorial on sample output. Section B (“NBO User's Guide”) is for the experienced user who has an installed program and general familiarity with standard default NBO output. This section documents the many keywords that can be used to alter and extend standard NBO job options, with examples of the resulting output. Section B is mandatory for users who wish to use the program to its full potential. This section describes keyword-controllable capabilities of the basic NBO modules (Sec. B.1-B.6) and GenNBO stand-alone program (Sec. B.7), as well as NBO- based supplemental modules (Sec. B.8 et seq.). The NBO website <http://nbo7.chem.wisc.edu/> provides additional tutorials, sample input and output for main program keywords, and explanatory background and bibliographic material to supplement this Manual. A quick-reference index to NBO keywords and keylists discussed in this manual is presented in Table 1 below. The table lists default (in [brackets]) and optional keywords, indicating whether additional parameters must be provided (Parms? Y = yes; N = no; opt. = optional) with a brief summary of the keyword result and the page number of the Manual for further reference. iv Table 1: NBO Keyword/Keylist Quick Summary Keyword Parms? Keyword Description Page Main Program Options [BEND] opt. Hybrid directionality and “bond-bending” A-25 analysis B-7 CMO opt. Bonding character of canonical molecular B-142 orbitals DIPOLE opt. Dipole moment analysis B-8, 34 [E2PERT] opt. 2nd-order perturbative estimates of NBO A-26 interactions B-7 MATRIX Y General operator and transformation matrix B-192 MEMORY Y Allocate dynamic memory B-6 NBBP opt. Natural bond-bond polarizability indices B-103 NBCP N Natural bond critical point analysis B-170 [NBO] opt. Natural bond orbital compositions A-21 B-5 [NBOSUM] N NBO summary table A-27 B-5 NCE N Natural coulomb electrostatics analysis B-181 NCS opt. Natural chemical shielding analysis B-147 NCU opt. Natural cluster unit analysis B-185 NJC opt. Natural J-coupling analysis B-155 NLMO N Natural localized molecular orbital B-5, 32 compositions [NPA] opt. Natural population analysis A-18 B-5 NPEPA opt. Natural poly-electron population analysis B-207 NRT N Natural resonance theory analysis B-82 PROP Y General 1e property analysis B-189 v RADICAL N Effectively unpaired electron distribution B-199 RDM2 N 2nd Order Reduced Density Matrix B-218 RNBO N Resonance Natural Bond Orbital B-222 STERIC opt. Natural steric analysis B-106 Control Options AOINFO N Write AO basis information to LFN 31 B-14 ARCHIVE opt. Write ARCHIVE (FILE47) for stand-alone B-14, GenNBO input 68 BNDIDX N NAO-Wiberg Bond Index and related valency B-14, indices 39 BOAO opt.
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