World Scientific Series in 20th Century Chemistry - Vol. 7

FRONTIER ORBITALS

AND

REACTION PATHS

Selected Papers of Kenichi Fukui

Editors

Kenichi Fukui Institute for Fundamental Chemistry

Hiroshi Fujimoto Division of Molecular Engineering,

Kyoto University

V|8% World Scientific w l Singapore • New Jersey L ondon • Hong Kong

CONTENTS

Preface vii

Introductory Remarks to the Frontier Orbital Theory 1

Part I. The Concept and Formulation 25

1. A Molecular Orbital Theory of Reactivity in Aromatic 29 Hydrocarbons (K. Fukui, T. Yonezawa, and H. Shingu) /. Chem. Phys., 20, 722-725, 1952.

2. Molecular Orbital Theory of Orientation in Aromatic, 33 Heteroaromatic, and Other Conjugated Molecules (K. Fukui, T. Yonezawa, C. Nagata, and H. Shingu) /. Chem. Phys., 22, 1433-1442, 1954.

3. Interrelations of Quantum-Mechanical Quantities Concerning 43 Chemical Reactivity of Conjugated Molecules (K. Fukui, T. Yonezawa, and C. Nagata) J. Chem. Phys., 26, 831-841, 1957.

4. MO-Theoretical Approach to the Mechanism of Charge-Transfer 54 in the Process of Aromatic Substitutions (K. Fukui, T. Yonezawa, and C. Nagata) J. Chem. Phys., 27, 1247-1259, 1957.

5. Novel Perturbation Theory in Simple LCAO Treatment of 67 Conjugated Molecules — Method of Perturbed Secular Determinant (K. Fukui, C. Nagata, T. Yonezawa, H. Kato and K. Morokuma) J. Chem. Phys., 31, 287-293, 1959.

6. Expansion Formulae of Secular Determinant in Simple 74 LCAO MO Treatment of Aromatic Hydrocarbons (K. Fukui, C. Nagata, T. Yonezawa, and A. Imamura) Bull. Chem. Soc. Jpn., 32, 450-451, 1959.

x Frontier Orbitals & Reaction Paths

7. A Further Study of Simple LCAO MO Perturbation Treatment 76 of Conjugated Molecules (K. Fukui, K. Morokuma, T. Yonezawa, and C. Nagata) Bull. Chem. Soc. Jpn., 33, 963-973, 1960.

8. Charge Transfer Mechanism of Reaction of Conjugated Molecules 87 (K. Fukui, K. Morokuma, T. Yonezawa, and C. Nagata) J. Chem. Phys., 32, 1743-1747, 1960.

9. A Quantum-mechanical Approach to the Theory of Aromaticity 92 (K. Fukui, A. Imamura, T. Yonezawa, and C. Nagata) Bull. Chem. Soc. Jpn., 33, 1591-1599, 1960.

10. A Theoretical Treatment of Molecular Complexes. 101 I. Silver-Aromatic Hydrocarbon Complexes (K. Fukui, A. Imamura, T. Yonezawa, and C. Nagata) Bull. Chem. Soc. Jpn., 34, 1076-1080, 1961.

11 A New Quantum-mechanical Reactivity Index for Saturated 106 Compounds (K. Fukui, H. Kato, and T. Yonezawa) Bull. Chem. Soc. Jpn., 34, 1111-1115, 1961.

12. An Attempt to Discuss Reactivities of Excited Molecules by 111 the Molecular Orbital Method (K. Fukui, K. Morokuma, and T. Yonezawa) Bull. Chem. Soc. Jpn., 34, 1178-1184, 1961.

13. Electronic Structure and Carcinogenic Activity of Aromatic 118 Compounds I. Condensed Aromatic Hydrocarbons (C. Nagata, K. Fukui, T. Yonezawa, and Y Tagashira) Cancer Research, 15, 233-239, 1955.

14. A Simple Quantum-Theoretical Interpretation of the Chemical 125 Reactivity of Organic Compounds (K. Fukui) P.-O. Löwdin and B. Pullman, eds., "Molecular Orbitals in Chemistry, Physics, and Biology",Academic Press, pp. 513-537, 1964.

Contents xi

15. The Role of Frontier Orbitals in Chemical Reactions 150 (K. Fukui) Nobel Lecture,pp. 146-166, 1982.

16. Intermolecular Interactions and Chemical Reactivity 171 (H. Fujimoto and K. Fukui) G. Klopman, ed., "Chemical Reactivity andReaction Paths", Wiley-Interscience, pp. 23-54, 1974.

17. Chemical Reactivity Theory — Its Pragmatism and Beyond 203 (K. Fukui) Pure&Appl. Chem., 54, 1825-1836, 1982.

Part IL Stereoselection 215 18. An MO-Theoretical Illumination for the Principle of 219

Stereoselection (K. Fukui) Bull. Chem. Soc. Jpn., 39,498-503, 1966.

19. Sigma-Pi Interaction Accompanied by Stereoselection 225 (K. Fukui and H. Fujimoto)

.Bull. Chem. Soc. Jpn., 39, 2116-2126, 1966.

20. The Stereoselection Rule for Electrocyclic Interactions 236 (K. Fukui and H. Fujimoto) Bull. Chem. Soc. Jpn., 40, 2018-2025, 1967.

21. Recognition of Stereochemical Paths by Orbital Interaction 244 (K. Fukui) Acc. Chem. Res., 4, 57-64, 1971.

Part III. Theoretical Aspects of Chemical Reactions 253 22. An MO-theoretical Interpretation of the Nature of Chemical 257

Reactions. I. Partitioning Analysis of the Interaction Energy (K. Fukui and H. Fujimoto) Bull. Chem. Soc. Jpn., 41, 1989-1997, 1968.

xii Frontier Orbitals & Reaction Paths

23. An MO-theoretical Interpretation of the Nature of Chemical 266 Reactions. II. The Governing Principles (K. Fukui and H. Fujimoto) Bull. Chem. Soc. Jpn., 42, 3399-3409, 1969.

24. Molecular Orbital Calculation of Chemically Interacting Systems. 277 Interaction between Radical and Closed-Shell Molecules (H. Fujimoto, S. Yamabe, T. Minato, and K. Fukui) /. Am. Chem. Soc, 94, 9205-9210, 1972.

25. Molecular Orbital Calculations of the Electronic Structure 283 of Borazane (H. Fujimoto, S. Kato, S. Yamabe, and K. Fukui) /. Chem. Phys., 60, 572-578, 1974.

26. An Orbital Interaction Rationale for the Role of Catalysts 290 (K. Fukui and S. Inagaki) J. Am. Chem. Soc, 97, 4445-4452, 1975.

27. Chemical Pseudoexcitation and Paradoxical Orbital 298 Interaction Effect (S. Inagaki, H. Fujimoto, and K. Fukui) J. Am. Chem. Soc, 97, 6108-6116, 1975.

28. On the Donor-Acceptor Relationship in Cyclic Additions 307 (H. Fujimoto, S. Inagaki, and K. Fukui) J. Am. Chem. Soc, 98, 2670-2671, 1976.

29. Orbital Mixing Rule 309 (S. Inagaki, H. Fujimoto, and K. Fukui) J. Am. Chem. Soc, 98, 4054-4061, 1976.

30. Orbital Interactions in Three Systems 317 (S. Inagaki, H. Fujimoto, and K. Fukui) J. Am. Chem. Soc, 98, 4693-4701, 1976.

Contents xiii

31. An MO-Theoretical Treatment of the Cationic Ring-Opening 326 Polymerisation, I. Ethylene Oxide (G. Frenking, H. Kato, and K. Fukui) Bull. Chem. Soc. Jpn., 48, 6-12, 1975.

32. A Theoretical Study on Biradicals. I. Theoretical Characteristics 333 of Biradicals (K. Fukui and K. Tanaka) Bull. Chem. Soc. Jpn., 50, 1391-1398, 1977.

33. A Molecular Orbital Calculation of Chemically Interacting 341 Systems. Interaction between Two Radicals (T. Minato, S. Yamabe, H. Fujimoto, and K. Fukui) Bull. Chem. Soc. Jpn., 51, 1-10, 1978.

34. A Molecular Orbital Theoretical Study on (SN)2 Molecules at 351 the Initial Stage of Polymerization to (SN)X. (T. Yamabe, K. Tanaka, K. Fukui, and H. Kato) J. Phys. Chem., 81, 727-731, 1977.

35. Orbital Interaction in the Dimerization of Disulfur Dinitride 356 to Tetrasulfur Tetranitride (K. Tanaka, T. Yamabe, A. Noda, K. Fukui, and H. Kato) J. Phys. Chem., 82, 1453-1454, 1978.

36. Electronic Behavior of Amorphous Chalcogenide Models 358 (A. Tachibana, T. Yamabe, M. Miyake, K. Tanaka, H. Kato, and K. Fukui) J. Phys. Chem., 82, 272-277, 1978.

37. Orbital Interaction in the Cycloaddition Reactions of Tetrasulfur 364 Tetranitride, Tetraarsenic Tetrasulfide, and Tetraarsenic Tetraselenide with Olefins (T. Yamabe, K. Tanaka, A. Tachibana, K. Fukui, and H. Kato) J. Phys. Chem., 83, 767-769, 1979.

xiv Frontier Orbitals & Reaction Paths

Part IV. Reaction Coordinate 38. A Formulation of the Reaction Coordinate

(K. Fukui) J. Phys. Chem., 74,4161-4163, 1970.

39. The Charge and Spin Transfers in Chemical Reaction Paths 374 (K. Fukui) R. Daudel and B. Pullman, eds., "The World of Quantum Chemistry", Reidel,pp. 113-141,1974.

40. Constituent Analysis of the Potential Gradient Along a Reaction 403 Coordinate. Method and an Application to CH4 + T Reaction (K. Fukui, S. Kato, and H. Fujimoto) J. Am. Chem. Soc, 97, 1-7, 1975.

41. Reaction Ergodography. Methane-Tritium Reaction 410 (S. Kato and K. Fukui) J. Am. Chem. Soc, 98, 6395-6397, 1976.

42. A Theoretical Treatment on the Behavior of the Hydrogen- 413 Bonded Proton in Malonaldehyde (S. Kato, H. Kato, and K. Fukui) J. Am. Chem. Soc, 99, 684-691, 1977.

43. Intrinsic Dynamism in Chemically Reacting Systems 421 (A. Tachibana and K. Fukui) Theor. Chim. Acta, 51, 189-206, 1979.

44. Intrinsic Field Theory of Chemical Reactions 439 (A. Tachibana and K. Fukui) Theor. Chim. Acta, 51, 275-296, 1979.

45. Variational Principles in a Chemical Reaction 461 (K. Fukui) Int. J. Quantum Chem., 15, 633-642, 1981.

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Contents xv

46. The Path of Chemical Reactions — The IRC Approach 471 (K. Fukui) Acc. Chem. Res., 14, 363-368, 1981.

Part V. A New Development 477

47. Interaction Frontier Orbitals 481 (K. Fukui, N. Koga, and H. Fujimoto) /. Am. Chem. Soc, 103, 196-197, 1981.

48. A Coupled Fragment Molecular Orbital Method for 483 Interacting Systems (H. Fujimoto, N. Koga, and K. Fukui) J. Am. Chem. Soc, 103, 7452-7457, 1981.

49. Reminiscences - My Forty Years' Study of Chemical Reactions 489 (K. Fukui) V. H. Smith, Jr. et al., eds., "Applied Quantum Chemistry", Reidel, pp. 1-25, 1986.

Part VI. OtherTopics

50. On the Behavior of the Excess Electron in Methane (S. Ishimaru, T. Yamabe, K. Fukui, and H. Kato) J. Phys. Chem., 78, 148-152, 1974.

51. Calculations of the Pseudopotential for the Excess Electron 522 in Water and Methane (S. Ishimaru, K. Fukui, and H. Kato) Theoret. Chim. Acta, 39, 103-110, 1975.

52. Theory of Decaying States Based on a Method of Coupled 530 Equations: Kapur-Peierls and Siegert Resonant States and the 'Extended' Hellmann-Feynman Theorem (A. Tachibana, T. Yamabe, and K. Fukui) J. Phys. B:Atom. Molec. Phys., 10, 3175-3188, 1977.

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