Intramolecular electron transfer, with bridge assistance and without, in molecules and models

Hale, Paul D.; Ratner, Mark A.

doi:10.1002/qua.560260822

Cited by 13 publications

(1 citation statement)

References 73 publications

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“…Besides the aesthetic motivation for pursuing this goal, it has become apparent that the deeper understanding reveals new aspects of the control of chemical reaction rates by the molecular environment. An example of this is the emerging picture of the interplay between molecular dynamical control (see ref 1-10, for example) and electronic control (see ref [11][12][13][14][15][16][17][18][19][20] in electron-transfer and biomolecular reactions.…”

Section: Introductionmentioning

confidence: 99%

Classical and quantum pictures of reaction dynamics in condensed matter: resonances, dephasing, and all that

Onuchic¹,

Wolynes²

1988

J. Phys. Chem.

223

102

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A remarkably rich picture of the dynamics of chemical reactions in condensed-phase systems has emerged in recent years. The interplay of friction, electronic nonadiabaticity, and intramolecular energy flow have been elucidated by use of pictures based on classical trajectories. We review the qualitative ideas of that picture. There are some significant limitations of that approach to reaction dynamics that arise from quantum interference effects. Using a trajectory picture along with the quantum superposition principle, we give qualitative arguments describing how the transmission coefficient for nonadiabatic barrier crossing can be affected by resonances. We highlight the connections and differences between classical friction and quantum mechanical dephasing effects in barrier crossing. We also discuss the relation of this trajectory-based picture and the traditional language of radiationless processes based on the Golden Rule and master equations.

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Section: Introductionmentioning

confidence: 99%

Classical and quantum pictures of reaction dynamics in condensed matter: resonances, dephasing, and all that

Onuchic¹,

Wolynes²

1988

J. Phys. Chem.

223

102

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Solvent Induced Intramolecular Electron Exchange Kinetics in 1,3‐Isodisubstituted Aromatic Radical Anions II. Activation Parameters

Grampp¹,

Shohoji²,

Herold³

et al. 1990

Ber Bunsenges Phys Chem

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From the alternant line broadening effect in the ESR‐spectra of the radical anions of 1,3‐dinitrobenzene and benzene‐1,3‐dicarbaldehyde in various protic and aprotic solvents the rates of intramolecular electron exchange were determined in the temperature range 260–340 K. Using Marcus theory and the Rips‐Jortner approach for the uniform adiabatic limit of electron transfer it is shown that the amount of transferred charge ze0 decreases with increasing temperature. This result is explained on the basis of the effect of temperature on the specific asymmetric solvation of the anions. For the 1,3‐dinitrobenzene radical anion in protic solvents the charge transfer number z changes slightly from 0.96 to 0.90 within 250–340 K and in aprotic solvents from 0.55 to 0.32 within 280–340 K. For benzene‐1,3‐dicarbaldehyde radical anion in protic solvents z changes from 0.40 to 0.29 within 260–320 K. From the measured activation parameters for the intramolecular electron exchange the values for the inner sphere reorganization energies λi were estimated, using values for the outer sphere reorganization λ0 as obtained by applying an ellipsoidal cavity model to the measured solvent dependence of the rates. For the 1,3‐dinitrobenzene radical anion λ0 increases with the degree of solvent association (from 18.4 to 106.4 kJ/mol), whereas λi varies much less (82.4–116.0 kJ/mol) for all protic and aprotic solvents investigated. From the difference in λ0 for protic and aprotic solvents, the value for the energy of solvation of the anions by hydrogen bonding is obtained as ≈ 10 kJ/mol.

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Electron transfer reactions dynamically coupled to a dielectric medium: Orientational effects and bridge assistance

Mikkelsen

Ratner

1987

Int. J. Quantum Chem.

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A new treatment for studying electron transfer reactions is considered. The treatment allows for a detailed description of the electronic structure and is therefore appropriate for a complete description of weakly interacting electron transfer reactions. The initial state for the electron transfer system is selected by a variational scheme. The electron transfer is pictured to take place in an encounter complex consisting of the donor, the acceptor, and (optionally) a solvenubridge molecule. The electronic structure of the encounter complex is dynamically coupled to the surrounding solvent, and the direct time evolution of the electron transfer system is followed by a nonlinear time-dependent Hartree-Fock method. We present examples with benzeneanion radical as the donor, pyridine as the acceptor, and water as the bridgekolvent molecule. The general formalism appears to be a useful approach for studying electron transfer reactions in solution.

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Intramolecular electron transfer, with bridge assistance and without, in molecules and models

Cited by 13 publications

References 73 publications

Classical and quantum pictures of reaction dynamics in condensed matter: resonances, dephasing, and all that

Classical and quantum pictures of reaction dynamics in condensed matter: resonances, dephasing, and all that

Solvent Induced Intramolecular Electron Exchange Kinetics in 1,3‐Isodisubstituted Aromatic Radical Anions II. Activation Parameters

Electron transfer reactions dynamically coupled to a dielectric medium: Orientational effects and bridge assistance

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