The Quantum Dynamical Basis of a Classical Kinetic Scheme Describing Coherent and Incoherent Regimes of Radical Pair Recombination
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Nikita N. Lukzen
Abstract
In recent work from this group (J. H. Klein et al. J. Am. Chem. Soc. 2015, 137, 11011), the magnetic field dependent charge recombination kinetics in donor/Ir-complex/acceptor triads has been determined with outstanding accuracy and reproducibility. The field-dependent kinetics has been analyzed in terms of a classical reaction scheme including the field-independent rate parameters of singlet recombination (rate constant kS) and S/T0 mixing (rate constant kST0) and the field-dependent rate constant k±(B) connecting central and outer Zeeman levels. In the present work, the extraction of k± from the experimental data is more precisely defined and the appearance of a “coherent” and “incoherent” regime of spin motion in a double log plot of k± vs. B is confirmed. The experimental decay curves have been reproduced by a full quantum dynamical model based on the stochastic Liouville equation, which was solved numerically, taking into account isotropic hyperfine coupling with five nuclear spins (1 N on donor radical, 4 H on acceptor radical) and anisotropic hyperfine coupling with the nitrogen nucleus at the donor radical. The results of the quantum calculations serve as a rigorous basis of interpreting the classical parameter k±. Furthermore, it is demonstrated that the incoherent part of spin motion is essential for a full understanding of the charge recombination kinetics even in the “coherent” regime.
Dedicated to: Professor Kev Salikhov on the occasion of his 80th birthday.
Acknowledgements
We gratefully acknowledge the help of Prof. Dr. Christine Peter and Dr. Stefan Gerlach in accessing the Scientific Compute Cluster (SCC) at the University of Konstanz. N. L. thanks the Alexander-von-Humboldt Foundation for financial support allowing his visit to Konstanz. N. L. is grateful to the Russian Foundation for Basic Research (grant No. 14-03-00453 А). The work at Würzburg was supported by the DFG (GRK 2112).
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©2017 Walter de Gruyter GmbH, Berlin/Boston
Artikel in diesem Heft
- Frontmatter
- Preface
- Editorial Review
- From Free Radicals and Spin-Chemistry Over Spin-Dynamics and Hyperpolarization to Biology and Materials Science
- On Relations Between Singlet and Triplet Recombination Yields for Singlet and Triplet Precursors
- The Quantum Dynamical Basis of a Classical Kinetic Scheme Describing Coherent and Incoherent Regimes of Radical Pair Recombination
- Reaction Operators for Radical Pairs. The Exactly Solvable Model
- Estimation of the Fraction of Spin-Correlated Radical Ion Pairs in Irradiated Alkanes using Magnetosensitive Recombination Luminescence from Exciplexes Generated upon Recombination of a Probe Pair
- Theoretical Description of Pulsed RYDMR: Refocusing Zero-Quantum and Single Quantum Coherences
- A Transient EPR Study of Electron Transfer in Tetrathiafulvalene-Aluminum(III) Porphyrin-Anthraquinone Supramolecular Triads
- Solvent Radical Anions in Irradiated Aliphatic Ketones and Esters as Observed Using Time-Resolved Magnetic Field Effects in the Recombination Fluorescence
- Effect of Dehydrated Trehalose Matrix on the Kinetics of Forward Electron Transfer Reactions in Photosystem I
- Photo-CIDNP in the Reaction Center of the Diatom Cyclotella meneghiniana Observed by 13C MAS NMR
- Light-Stimulated Generation of Free Radicals by Quinones-Chelators
- Influence of C2-Methylation of Imidazolium Based Ionic Liquids on Photoinduced Spin Dynamics of the Dissolved ZnTPP Studied by Time-Resolved EPR
- ESR Study of Electron States in Ge/Si Heterostructures with Nanodisc Shaped Quantum Dots
- Novel Anthrathiophene-Based Small Molecules as Donor Material for Organic Photovoltaics: Synthesis and Light-Induced EPR Study
- Structural Determination of a DNA Oligomer for a Molecular Spin Qubit Lloyd Model of Quantum Computers
Artikel in diesem Heft
- Frontmatter
- Preface
- Editorial Review
- From Free Radicals and Spin-Chemistry Over Spin-Dynamics and Hyperpolarization to Biology and Materials Science
- On Relations Between Singlet and Triplet Recombination Yields for Singlet and Triplet Precursors
- The Quantum Dynamical Basis of a Classical Kinetic Scheme Describing Coherent and Incoherent Regimes of Radical Pair Recombination
- Reaction Operators for Radical Pairs. The Exactly Solvable Model
- Estimation of the Fraction of Spin-Correlated Radical Ion Pairs in Irradiated Alkanes using Magnetosensitive Recombination Luminescence from Exciplexes Generated upon Recombination of a Probe Pair
- Theoretical Description of Pulsed RYDMR: Refocusing Zero-Quantum and Single Quantum Coherences
- A Transient EPR Study of Electron Transfer in Tetrathiafulvalene-Aluminum(III) Porphyrin-Anthraquinone Supramolecular Triads
- Solvent Radical Anions in Irradiated Aliphatic Ketones and Esters as Observed Using Time-Resolved Magnetic Field Effects in the Recombination Fluorescence
- Effect of Dehydrated Trehalose Matrix on the Kinetics of Forward Electron Transfer Reactions in Photosystem I
- Photo-CIDNP in the Reaction Center of the Diatom Cyclotella meneghiniana Observed by 13C MAS NMR
- Light-Stimulated Generation of Free Radicals by Quinones-Chelators
- Influence of C2-Methylation of Imidazolium Based Ionic Liquids on Photoinduced Spin Dynamics of the Dissolved ZnTPP Studied by Time-Resolved EPR
- ESR Study of Electron States in Ge/Si Heterostructures with Nanodisc Shaped Quantum Dots
- Novel Anthrathiophene-Based Small Molecules as Donor Material for Organic Photovoltaics: Synthesis and Light-Induced EPR Study
- Structural Determination of a DNA Oligomer for a Molecular Spin Qubit Lloyd Model of Quantum Computers
