Reviews in Computational Chemistry Volume 18

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206 Charge-Transfer Reactions in Condensed Phases of the ET free energy surfaces to the solvent-induced component of the optical Franck–Condon provides a unique possibility to apply the statistical mechanical analysis of ET and CT energetics and to test it on experiment. The band shape analysis of optical profiles is thus the key factor in a successful interplay between theory and experiment. This chapter outlines some recent advances in the statistical mechanical analysis of the CT energetics. The basic strategy used in this approach is to introduce new physical features of CT activation into the system Hamiltonian used to build the free energy surfaces. These are then applied to calculate the Franck–Condon factors and determine how the changes in the physics of the problem affect the optical observables. This development highlights two fundamental results. First, the MH model of fixed charges solvated in a dense, condensed-phase environment leads to a very accurate representation of the ET energetics in terms of two intersecting parabolas. The static nonlinear solvation effects are generally weak and do not substantially distort the parabolas. There is, however, ample room to modify the free energy surfaces when changes in the electronic density of the donor–acceptor complex are allowed either through polarizability or electronic delocalization. The CT free energies then inherit nonlinear features, and a number of interesting consequences for optical observables can be anticipated. These fascinating phenomena will be the subject of future research. ACKNOWLEDGMENTS D.V.M. acknowledges the support by the Department of Chemistry and Biochemistry at ASU and partial support by the Petroleum Research Fund, administered by the American Chemical Society, (36404-G6). G.A.V. acknowledges support from the Department of Energy, Basic Energy Sciences Program. REFERENCES 1. R. A. Marcus, Adv. Chem. Phys., 106, 1 (1999). Electron Transfer Past and Future. 2. P. F. Barbara and W. Jarzeba, Adv. Photochem., 15, 1 (1990). Ultrafast Photochemical Intramolecular Charge and Excited State Solvation. 3. B. Bagchi and N. Gayathri, Adv. Chem. Phys., 107, 1 (1999). Interplay Between Ultrafast Polar Solvation and Vibrational Dynamics in Electron Transfer Reactions: Role of High- Frequency Vibrational Modes. 4. B. Bagchi and R. Biswas, Adv. Chem. Phys., 109, 207 (1999). Polar and Nonpolar Solvation Dynamics, Ion Diffusion, and Vibrational Relaxation: Role of Biphasic Solvent Response in Chemical Dynamics. 5. F. O. Raineri and H. L. Friedman, Adv. Chem. Phys., 107, 81 (1999). Solvent Control of Electron Transfer Reactions. 6. N. S. Hush, Progr. Inorg. Chem., 8, 391 (1967). Intervalence-Transfer Absorption. Part 2. Theoretical Considerations and Spectroscopic Data. See also, R. S. Mulliken and W. B. Person, Molecular Complexes, Wiley, New York, 1969.
References 207 7. M. D. Newton, Adv. Chem. Phys., 106, 303 (1999). Control of Electron Transfer Kinetics: Models for Medium Reorganization and Donor–Acceptor Coupling. 8. J. J. Regan and J. N. Onuchic, Adv. Chem. Phys., 107, 303 (1999). Electron-Transfer Tubes. 9. L. D. Landau and E. M. Lifshits, Quantum Mechanics, Pergamon, Oxford, UK, 1965. 10. A. M. Kuznetsov, Charge Transfer in Chemical Reaction Kinetics, Presses Polytechniques et Universitaires Romandes, Lausanne, Switzerland, 1997. 11. J. Ulstrup, Charge Transfer Processes in Condensed Media, Springer, Berlin, 1979. 12. R. A. Marcus, Annu. Rev. Phys. Chem., 15, 155 (1964). Chemical and Electrochemical Electron-Transfer Theory. 13. C. Creutz, Progr. Inorg. Chem., 30, 1 (1980). Mixed Valence Complexes of d5 –d6 Metal Centers. 14. P. F. Barbara, T. J. Meyer, and M. A. Ratner, J. Phys. Chem., 100, 13148 (1996). Contemporary Issues in Electron Transfer Research. 15. M. Lax, J. Chem. Phys., 11, 1752 (1952). The Franck–Condon Principle and Its Application to Crystals. 16. P. Chen and T. J. Meyer, Chem. Rev., 98, 1439 (1998). Medium Effects on Charge Transfer in Metal Complexes. 17. M. Bixon and J. Jortner, Adv. Chem. Phys., 106, 35 (1999). Electron Transfer–From Isolated Molecules to Biomolecules. 18. R. A. Marcus, J. Phys. Chem., 93, 3078 (1989). Relation Between Charge Transfer Absorption and Fluorescence Spectra and the Inverted Region. 19. M. B. Robin and P. Day, Adv. Inorg. Chem. Radiochem., 10, 247 (1967). Mixed Valence Chemistry—A Survey and Classification. 20. S. F. Nelsen, Chem. Eur. J., 6, 581 (2000). ‘‘Almost Delocalized’’ Intervalene Compounds. 21. M. R. Wasielewski, Chem. Rev., 92, 435 (1992). Photoinduced Electron Transfer in Supermolecular Systems for Artificial Photosynthesis. 22. J. W. Verhoeven, Adv. Chem. Phys., 106, 603 (1999). From Close Contact to Long-Range Intramolecular Electron Transfer. 23. K. Y. Wong and P. N. Schatz, Progr. Inorg. Chem., 28, 369 (1981). A Dynamic Model for Mixed-Valence Compounds. 24. M. Born and K. Huang, Dynamic Theory of Crystal Lattices, Clarendon Press, Oxford, UK, 1985. 25. D. Chandler and P. Wolynes, J. Chem. Phys., 74, 4078 (1981). Exploring the Isomorphism Between Quantum Theory and Classical Statistical Mechanics of Polyatomic Fluids. 26. G. A. Voth, Adv. Chem. Phys., 93, 135 (1996). Path-Integral Centroid Methods in Quantum Statistical Mechanics and Dynamics. 27. S. I. Pekar, Research in Electron Theory of Crystals, United States Atomic Energy Commission, Washington, DC, 1963. 28. A. S. Alexandrov and N. Mott, Polarons and Bipolarons, World Scientific, Singapore, 1995. 29. A. B. Myers, Annu. Rev. Phys. Chem., 49, 267 (1998). Molecular Electronic Spectral Broadening in Liquids and Glasses. 30. K. Ando and J. T. Hynes, Adv. Chem. Phys., 110, 381 (1999). Acid–Base Proton Transfer and Ion Pair Formation in Solution. 31. H. J. Kim and T. J. Hynes, Am. Chem. Soc., 114, 10508 (1992). A Theoretical Model for SN1 Ionic Dissociation in Solution. 1. Activation Free Energetics. 32. A. Warshel and W. W. Parson, Annu. Rev. Phys. Chem., 42, 279 (1991). Computer Simulations of Electron-Transfer Reactions in Solution and in Photosynthetic Reaction Centers. 33. L. W. Ungar, M. D. Newton, and G. A. Voth, J. Phys. Chem. B, 103, 7367 (1999). Classical and Quantum Simulation of Electron Transfer Through a Polypeptide.
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Reviews in Computational Chemistry
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Kenny B. Lipkowitz Department of Ch
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vi Preface three-dimensional struct
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viii Preface some descriptors and i
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Epilogue and Dedication My associat
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Contents 1. Clustering Methods and
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Contents xv Electron Transfer in Po
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Contributors John M. Barnard, Barna
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Contributors to Previous Volumes *
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Volume 3 (1992) Tamar Schlick, Opti
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Volume 7 (1996) Geoffrey M. Downs a
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Volume 11 (1997) Mark A. Murcko, Re
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T. Daniel Crawford* and Henry F. Sc
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Topics Covered in Volumes 1-18 * Ab
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Reviews in Computational Chemistry
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2 Clustering Methods and Their Uses
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10 Clustering Methods and Their Use
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42 The Use of Scoring Functions in
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Table 1 Reference List for the Most
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CHAPTER 3 Potentials and Algorithms
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Vn (1 + cos(nω + γ)) 2 K θ (θ
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are modified by their environment w
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Table 1 Polarizability Parameters f
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The polarizable point dipole models
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two to three orders of magnitude sl
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M i z i + q i d i k i and shell cha
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Shell Models 103 on estimates of sh
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minimization can be replaced by mor
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The energy required to create a cha
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for all i ði:e:; 8 iÞ: @U @qi l
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where we have used q Cl ¼ qNa. The
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Electronegativity Equalization Mode
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Electronegativity Equalization Mode
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of N molecules is taken as a Hartre
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is treated using variable charges.
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water have been developed, includin
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Applications 123 classical and rigi
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developing polarizable models. A va
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Comparison of the Polarization Mode
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negligible errors in such propertie
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ecome significant at field strength
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noteworthy in this regard because t
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References 135 9. P. Cieplak and P.
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References 137 48. E. L. Pollock an
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References 139 Computational Chemis
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References 141 139. J. Hinze and H.
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References 143 178. J. J. P. Stewar
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References 145 216. M. W. Mahoney a
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CHAPTER 4 New Developments in the T
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Introduction 149 applications). For
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FCWD(∆E ) FCWD(0) ∆E = 0 ∆E
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Introduction 153 Equations [6]-[12]
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