Essentials of Computational Chemistry

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282 8 DENSITY FUNCTIONAL THEORY Table 8.1 (continued) Level <strong>of</strong> theory Test sets a W1 0.6 (2.2) W2 0.5 (1.9) A B C D E LSDA functionals SVWN/6-31G(d) 35.7 36.4 83.8 (84.0) SVWN/6-31G(d,p) 52.2 SVWN/TZ2P 50.1 SVWN/6-311+G(2df,p) 43.5 83.7 c 121.9 c (207.7) (347.5) GGA and MGGA functionals BB95/numeric 8.6 (28.6) BISM/6-311+G(3df,2p) 5.9 (21.8) BVWN/6-31G(d) 4.4 BKCIS/6-311+G(3df,2p) 8.2 14.6 (25.9) (39.6) BLYP/6-31G(d) 5.6 5.3 (18.8) BLYP/6-31G(d,p) 7.0 BLYP/6-31+G(d) 4.4 (16.3) BLYP/6-311G(2df,p) 9.6 BLYP/6-311+G(3df,2p) 5.0 7.3 9.3 (15.8) (28.4) BLYP/6-311++G(3df,3pd) 9.6 7.3 c 9.5 c BLYP/pVQZ 7.0d (27.8) (28.1) (41.0) BP86/6-31G(d) 7.2 (24.0) BP86/6-311+G(3df,2p) 10.3 20.1 c 26.3 c (25.4) (48.7) (72.7) BPW91/6-31G(d,p) 7.4 BPW91/TZ2P 7.3 BPW91/6-311+G(3df,2p) 7.8 (32.2) BPW91/6-311++G(3df,3pd) 6.0 8.0 c 9.0 c EDF1/6-31+G(d) 3.2 (15.3) (32.4) (28.0)
8.6 GENERAL PERFORMANCE OVERVIEW OF DFT 283 Table 8.1 (continued) Level <strong>of</strong> theory Test sets a A B C D E HCTH/6-311++G(3df,3pd) 5.6 c 7.2 c (28.0) (28.0) OLYP/pVQZ 5.5 d 4.8 c 5.9 c (23.6) (27.0) (27.0) PBE/6-311+G(3df,2p) 8.2 16.9 c 22.2 c (29.1) (50.5) (79.7) mPBE/6-311++G(3df,3pd) 4.6 6.3 (18.9) (27.5) PBEKCIS/6-311+G(3df,2p) 11.9 24.9 (35.2) (66.5) PKZB/6-311+G(3df,2p) 3.6 4.8 c 7.0 c (11.0) (39.8) (39.8) PKZBKCIS/6-311+G(3df,2p) 4.1 9.7 (14.4) (38.8) PWPW91/6-311++G(3df,3pd) 8.6 17.7 c 23.6 c (52.7) (81.1) mPWPW91/6-311++G(3df,3pd) 6.7 15.0 TPSS/6-311++G(3df,3pd) 6.0 c 5.8 c (22.9) (22.9) VSXC/6-311+G(3df,2p) 2.5 2.8 c 3.5 c (10.0) (11.5) (12.0) XLYP/6-311+G(3df,2p) 7.6 e Hybrid functionals BH&HLYP/6-311++G(3df,3pd) 11.7 21.7e (23.4) B0KCIS/6-311+G(3df,2p) 3.0 5.3 (10.5) (28.6) B1B95/numeric 2.0 (7.5) B1LYP/6-311++G(3df,3pd) 3.1 (12.2) B1PW91/6-311++G(3df,3pd) 5.4 (14.3) MPW1K/MG3S 11.0b PBE1PBE/6-311+G(3df,2p) 3.1 4.4b 4.9c 6.7c (10.7) (21.3) (35.6) PW1PW91/6-311+G(3df,2p) 5.3e mPW1PW91/6-311++G(3df,3pd) 3.5 4.2b 3.9e (6.7) TPSSh/6-311++G(3df,3pd) 4.2c 3.9c (22.0) (16.2) (continued overleaf )
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Essentials of Computational Chemist
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Essentials of Computational Chemist
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For Katherine
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viii CONTENTS 2.5 Menagerie of Mode
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x CONTENTS 7 Including Electron Cor
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xii CONTENTS 11.4 Strengths and Wea
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Preface to the First Edition Comput
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PREFACE TO THE FIRST EDITION xvii d
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xx PREFACE TO THE SECOND EDITION to
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Known Typographical and Other Error
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1 What are Theory, Computation, and
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Activation free energy (kcal mol
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1.3 COMPUTABLE QUANTITIES 5 etc.) f
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a a r 1 1.3 COMPUTABLE QUANTITIES 7
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1.3 COMPUTABLE QUANTITIES 9 path is
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1.4 COST AND EFFICIENCY 11 this is
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1.4 COST AND EFFICIENCY 13 kinds of
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Physical quantity (unit name) BIBLI
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2 Molecular Mechanics 2.1 History a
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2.2 POTENTIAL ENERGY FUNCTIONAL FOR
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2.3 FORCE-FIELD ENERGIES AND THERMO
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Heat of formation A E nb (A) 2.4 GE
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gradient vector, g, which is define
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Eq. (2.38) as 2.4 GEOMETRY OPTIMIZA
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2.4 GEOMETRY OPTIMIZATION 47 that t
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2.4 GEOMETRY OPTIMIZATION 49 is opp
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Table 2.1 Force fields Name (if any
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12 Davies, E. K. and Murrall, N. W.
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5 (MM2(85), MM2(91), Chem-3D) Compr
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2.5 MENAGERIE OF MODERN FORCE FIELD
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2.6 FORCE FIELDS AND DOCKING 63 Fig
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2.7 CASE STUDY: (2R ∗ ,4S ∗ )-1
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REFERENCES 67 Cramer, C. J. 1994.
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3 Simulations of Molecular Ensemble
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3.2 PHASE SPACE AND TRAJECTORIES 71
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m −b r eq −b 3.3 MOLECULAR DYNA
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and 3.3 MOLECULAR DYNAMICS 75 p(t +
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3.3 MOLECULAR DYNAMICS 77 step mean
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3.3 MOLECULAR DYNAMICS 79 of course
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3.4 MONTE CARLO 81 One way to reduc
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3.5 ENSEMBLE AND DYNAMICAL PROPERTY
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3.6 KEY DETAILS IN FORMALISM 89 Fig
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3.6 KEY DETAILS IN FORMALISM 91 alc
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3.6 KEY DETAILS IN FORMALISM 93 mor
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3.6 KEY DETAILS IN FORMALISM 95 der
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3.6 KEY DETAILS IN FORMALISM 97 to
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3.8 CASE STUDY: SILICA SODALITE 99
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BIBLIOGRAPHY AND SUGGESTED ADDITION
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REFERENCES 103 Jaqaman, K. and Orto
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106 4 FOUNDATIONS OF MOLECULAR ORBI
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132 5 SEMIEMPIRICAL IMPLEMENTATIONS
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166 6 AB INITIO HARTREE-FOCK MO THE
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204 7 INCLUDING ELECTRON CORRELATIO
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Page 324 and 325: 9 Charge Distribution and Spectrosc
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9.3 SPECTROSCOPY OF NUCLEAR MOTION
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Energy hn 0→1 9.3 SPECTROSCOPY OF
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9.4 NMR SPECTRAL PROPERTIES 345 The
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9.4 NMR SPECTRAL PROPERTIES 347 Tab
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9.5 CASE STUDY: MATRIX ISOLATION OF
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REFERENCES 351 The use of computed
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REFERENCES 353 Rablen, P. R., Pearl
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356 10 THERMODYNAMIC PROPERTIES of
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358 10 THERMODYNAMIC PROPERTIES whe
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360 10 THERMODYNAMIC PROPERTIES tha
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362 10 THERMODYNAMIC PROPERTIES (Th
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364 10 THERMODYNAMIC PROPERTIES the
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368 10 THERMODYNAMIC PROPERTIES Ene
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372 10 THERMODYNAMIC PROPERTIES 10.
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374 10 THERMODYNAMIC PROPERTIES gen
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382 10 THERMODYNAMIC PROPERTIES Tab
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384 10 THERMODYNAMIC PROPERTIES Clo
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386 11 IMPLICIT MODELS FOR CONDENSE
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12 Explicit Models for Condensed Ph
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12.2 COMPUTING FREE-ENERGY DIFFEREN
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∆G 12.2 COMPUTING FREE-ENERGY DIF
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12.4 SOLVENT MODELS 445 In some cas
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12.4 SOLVENT MODELS 447 increases t
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12.5 RELATIVE MERITS OF EXPLICIT AN
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12.5 RELATIVE MERITS OF EXPLICIT AN
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12.6 CASE STUDY: BINDING OF BIOTIN
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REFERENCES 455 Levy, R. M. and Gall
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13 Hybrid Quantal/Classical Models
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13.2 BOUNDARIES THROUGH SPACE 459 a
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13.2 BOUNDARIES THROUGH SPACE 461 i
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13.2 BOUNDARIES THROUGH SPACE 463 T
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13.2 BOUNDARIES THROUGH SPACE 465 W
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13.3 BOUNDARIES THROUGH BONDS 467 t
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13.3 BOUNDARIES THROUGH BONDS 469 o
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180 180 4 10 15 15 20 150 6 8 150 8
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13.3 BOUNDARIES THROUGH BONDS 473 O
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13.3.3 Frozen Orbitals 13.3 BOUNDAR
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Link atom LSCF GHO 13.4 EMPIRICAL V
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13.4 EMPIRICAL VALENCE BOND METHODS
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13.4 EMPIRICAL VALENCE BOND METHODS
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13.5 CASE STUDY: CATALYTIC MECHANIS
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REFERENCES 485 Gao, J., Amara, P.,
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14 Excited Electronic States 14.1 D
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14.1 DETERMINANTAL/CONFIGURATIONAL
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14.1 DETERMINANTAL/CONFIGURATIONAL
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14.2 SINGLY EXCITED STATES 493 and
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14.2 SINGLY EXCITED STATES 495 Tabl
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14.2 SINGLY EXCITED STATES 497 wher
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14.3 GENERAL EXCITED STATE METHODS
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14.3 GENERAL EXCITED STATE METHODS
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14.4 SUM AND PROJECTION METHODS 503
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14.4 SUM AND PROJECTION METHODS 505
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14.5 TRANSITION PROBABILITIES 507 o
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14.5 TRANSITION PROBABILITIES 509 I
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14.6 SOLVATOCHROMISM 511 overlap) l
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14.7 CASE STUDY: ORGANIC LIGHT EMIT
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BIBLIOGRAPHY AND SUGGESTED ADDITION
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REFERENCES 517 Kim, K., Shavitt, I,
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520 15 ADIABATIC REACTION DYNAMICS
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Appendix A Acronym Glossary Note: B
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ACRONYM GLOSSARY 551 ECP Effective
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ACRONYM GLOSSARY 553 mPW1S mPW1PW91
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ACRONYM GLOSSARY 555 SF-CISD Spin-f
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558 APPENDIX B H 3 C CH 3 H H H a
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560 APPENDIX B Linear molecule? no
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562 APPENDIX B Table B.5 Product ru
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Appendix C Spin Algebra C.1 Spin Op
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function we have SPIN ALGEBRA 567
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SPIN ALGEBRA 569 + = 1 1 ( 2 2 α(
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C.3 UHF Wave Functions SPIN ALGEBRA
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SPIN ALGEBRA 573 = 〈cs s |H |cs s
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Appendix D Orbital Localization D.1
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ORBITAL LOCALIZATION 577 〈|H |〉
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E rel (kcal mol −1 ) 10 8 6 4 2 0
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582 INDEX B3PW91, 266-267, 284, 288
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584 INDEX Convergence (continued) f
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Global minimum, 23, 46, 97, 146, 38
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Matrix diagonalization, (see also S
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primitive, 168-173 Slater-type, 134
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Reductive dechlorination, 422-424 R
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SYBYL, 58 Symmetry, 182-188, 209, 2
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