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Title: Spin polarization transfer by the radical pair mechanism

Abstract

In a three-site representation, we study a spin polarization transfer from radical pair spins to a nearby electron or nuclear spin. The quantum dynamics of the radical pair spins is governed by a constant exchange interaction between the radical pair spins which have different Zeeman frequencies. Radical pair spins can recombine to the singlet ground state or to lower energy triplet states. It is then shown that the coherent dynamics of the radical pair induces spin polarization on the nearby third spin in the presence of a magnetic field. The spin polarization transfer depends on the difference between Zeeman frequencies, the singlet and triplet recombination rates, and on the exchange and dipole-dipole interactions between the different spins. Specifically, the sign of the polarization depends on the exchange coupling between radical pair spins and also on the difference between singlet and triplet recombination rate constants.

Authors:
 [1];  [1];  [1]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry, and Argonne-Northwestern Solar Energy Research (ANSER) Center
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington D.C. (United States). Center for Bio-Inspired Energy Science (CBES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1370623
Grant/Contract Number:  
SC0000989
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 5; Related Information: CBES partners with Northwestern University (lead); Harvard University; New York University; Pennsylvania State University; University of Michigan; University of Pittsburgh; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; catalysis (homogeneous); solar (photovoltaic); bio-inspired; charge transport; mesostructured materials; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly)

Citation Formats

Zarea, Mehdi, Ratner, Mark A., and Wasielewski, Michael R. Spin polarization transfer by the radical pair mechanism. United States: N. p., 2015. Web. doi:10.1063/1.4927589.
Zarea, Mehdi, Ratner, Mark A., & Wasielewski, Michael R. Spin polarization transfer by the radical pair mechanism. United States. doi:10.1063/1.4927589.
Zarea, Mehdi, Ratner, Mark A., and Wasielewski, Michael R. Mon . "Spin polarization transfer by the radical pair mechanism". United States. doi:10.1063/1.4927589. https://www.osti.gov/servlets/purl/1370623.
@article{osti_1370623,
title = {Spin polarization transfer by the radical pair mechanism},
author = {Zarea, Mehdi and Ratner, Mark A. and Wasielewski, Michael R.},
abstractNote = {In a three-site representation, we study a spin polarization transfer from radical pair spins to a nearby electron or nuclear spin. The quantum dynamics of the radical pair spins is governed by a constant exchange interaction between the radical pair spins which have different Zeeman frequencies. Radical pair spins can recombine to the singlet ground state or to lower energy triplet states. It is then shown that the coherent dynamics of the radical pair induces spin polarization on the nearby third spin in the presence of a magnetic field. The spin polarization transfer depends on the difference between Zeeman frequencies, the singlet and triplet recombination rates, and on the exchange and dipole-dipole interactions between the different spins. Specifically, the sign of the polarization depends on the exchange coupling between radical pair spins and also on the difference between singlet and triplet recombination rate constants.},
doi = {10.1063/1.4927589},
journal = {Journal of Chemical Physics},
number = 5,
volume = 143,
place = {United States},
year = {2015},
month = {8}
}

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Cited by: 5 works
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Works referenced in this record:

Chemical compass model of avian magnetoreception
journal, April 2008

  • Maeda, Kiminori; Henbest, Kevin B.; Cintolesi, Filippo
  • Nature, Vol. 453, Issue 7193
  • DOI: 10.1038/nature06834

Magnetic field dependence of intramolecular exciplex formation in polymethyelene-linked A–D systems
journal, July 1985


A novel radical-triplet pair mechanism for chemically induced electron polarization (CIDEP) of free radicals in solution
journal, March 1990


Electron paramagnetic resonance of spin-correlated radical pairs in photosynthetic reactions
journal, July 1987


Interaction between Polarized Triplets and Stable Radicals in Liquid Solutions
journal, May 2001

  • Blank, Aharon; Levanon, Haim
  • The Journal of Physical Chemistry A, Vol. 105, Issue 20
  • DOI: 10.1021/jp010033g

The triplet state in bacterial photosynthesis: Possible mechanisms of the primary photo-act
journal, September 1975

  • Thurnauer, M. C.; Katz, J. J.; Norris, J. R.
  • Proceedings of the National Academy of Sciences, Vol. 72, Issue 9
  • DOI: 10.1073/pnas.72.9.3270

The relaxational mechanism of net CIDEP generation in triplet—radical quenching
journal, June 1993


EPR of spin-correlated radical pairs. Analytical treatment of selective excitation including zero-quantum coherence
journal, February 1993


Time resolved electron spin resonance of spin correlated micelle confined radical pairs
journal, February 2000

  • Tarasov, V. F.; Forbes, M. D. E.
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 56, Issue 2
  • DOI: 10.1016/S1386-1425(99)00236-X

Electron spin emission spectra from pairs of radicals
journal, September 1973


Electron spin resonance of spin-correlated radical pairs
journal, April 1987


A static ensemble approximation for stochastically modulated quantum systems
journal, February 1989

  • Bittl, R.; Schulten, K.
  • The Journal of Chemical Physics, Vol. 90, Issue 3
  • DOI: 10.1063/1.456073

Electron–electron–nuclear three-spin mixing in spin-correlated radical pairs
journal, June 1997

  • Jeschke, Gunnar
  • The Journal of Chemical Physics, Vol. 106, Issue 24
  • DOI: 10.1063/1.474063

Field dependent CIDNP from photochemically generated radical ion pairs in rigid bichromophoric systems
journal, March 2001


A New Mechanism for Chemically Induced Dynamic Nuclear Polarization in the Solid State
journal, May 1998

  • Jeschke, Gunnar
  • Journal of the American Chemical Society, Vol. 120, Issue 18
  • DOI: 10.1021/ja973744u

Magnetic Field-Induced Switching of the Radical-Pair Intersystem Crossing Mechanism in a Donor−Bridge−Acceptor Molecule for Artificial Photosynthesis
journal, February 2011

  • Colvin, Michael T.; Ricks, Annie Butler; Scott, Amy M.
  • Journal of the American Chemical Society, Vol. 133, Issue 5
  • DOI: 10.1021/ja1094815

TREPR spectra of micelle-confined spin correlated radical pairs: I. Molecular motion and simulations
journal, January 2014

  • Tarasov, Valery F.; Jarocha, Lauren E.; Avdievich, Nikolai I.
  • Photochemical & Photobiological Sciences, Vol. 13, Issue 2
  • DOI: 10.1039/c3pp50328c

Theory of chemically induced dynamic electron polarization. I
journal, January 1973

  • Pedersen, J. Boiden
  • The Journal of Chemical Physics, Vol. 58, Issue 7
  • DOI: 10.1063/1.1679576

Analytic formula for chemically induced magnetic polarization by ST ±1 mixing in a strong magnetic field
journal, May 1980

  • Adrian, F. J.; Monchick, L.
  • The Journal of Chemical Physics, Vol. 72, Issue 10
  • DOI: 10.1063/1.439007

Analysis of anisotropic electron spin polarization in the photosynthetic bacterium Rhodospirillum rubrum.
journal, March 1993

  • Hore, P. J.; Riley, D. J.; Semlyen, J. J.
  • Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1141, Issue 2-3
  • DOI: 10.1016/0005-2728(93)90046-I

Spin polarization generated in the triplet-doublet interaction: hyperfine-dependent chemically induced dynamic electron polarization
journal, November 1991

  • Kawai, Akio; Okutsu, Tetsuo; Obi, Kinichi
  • The Journal of Physical Chemistry, Vol. 95, Issue 23
  • DOI: 10.1021/j100176a020

An electron spin polarization study of the interaction of photoexcited triplet molecules with mono- and polynitroxyl stable free radicals
journal, February 1993

  • Turro, Nicholas J.; Khudyakov, Igor V.; Bossmann, Stefan H.
  • The Journal of Physical Chemistry, Vol. 97, Issue 6
  • DOI: 10.1021/j100108a007

Biradical CIDNP and the dynamics of polymethylene chains
journal, September 1977

  • de Kanter, F. J. J.; den Hollander, J. A.; Huizer, A. H.
  • Molecular Physics, Vol. 34, Issue 3
  • DOI: 10.1080/00268977700102161

Simple rules for chemically induced dynamic nuclear polarization
journal, January 1971

  • Kaptein, R.
  • Journal of the Chemical Society D: Chemical Communications, Issue 14
  • DOI: 10.1039/c29710000732

Temperature dependence of the CIDEP spectrum of acetone
journal, January 1988

  • Tominaga, Keisuke; Yamauchi, Seigo; Hirota, Noboru
  • The Journal of Chemical Physics, Vol. 88, Issue 2
  • DOI: 10.1063/1.454182

Exchange effects and cidep
journal, September 1990

  • Jenks, William S.; Turro, Nicholas J.
  • Research on Chemical Intermediates, Vol. 13, Issue 3
  • DOI: 10.1163/156856790X00111

Memory of spin polarization in triplet-doublet systems
journal, December 1986

  • Imamura, Takashi; Onitsuka, Osamu; Obi, Kinichi
  • The Journal of Physical Chemistry, Vol. 90, Issue 26
  • DOI: 10.1021/j100284a001

Spin-polarized electron paramagnetic resonance spectra of radical pairs in micelles: observation of electron spin-spin interactions
journal, June 1987

  • Closs, Gerhard L.; Forbes, Malcolm D. E.; Norris, James R.
  • The Journal of Physical Chemistry, Vol. 91, Issue 13
  • DOI: 10.1021/j100297a026

Electron Spin Polarization Transfer from Excited Triplet Porphyrins to a Nitroxide Radical via a Spin Exchange Mechanism
journal, November 1995

  • Fujisawa, Jun-ichi; Ishii, Kazuyuki; Ohba, Yasunori
  • The Journal of Physical Chemistry, Vol. 99, Issue 47
  • DOI: 10.1021/j100047a006

TREPR spectra of micelle-confined spin correlated radical pairs: II. Spectral decomposition and asymmetric line shapes
journal, January 2014

  • Tarasov, Valery F.; Jarocha, Lauren E.; Forbes, Malcolm D. E.
  • Photochemical & Photobiological Sciences, Vol. 13, Issue 2
  • DOI: 10.1039/c3pp50329a

First observation of a radical-triplet pair mechanism (RTPM) with doublet precursor
journal, January 1992

  • Kawai, Akio; Obi, Kinichi
  • The Journal of Physical Chemistry, Vol. 96, Issue 1
  • DOI: 10.1021/j100180a014

Chemically induced dynamic electron polarization in pulse radiolysis. S-T.+-.1 polarization from hydrogen radical reactions
journal, January 1977

  • Trifunac, A. D.; Nelson, D. J.
  • Journal of the American Chemical Society, Vol. 99, Issue 1
  • DOI: 10.1021/ja00443a071

Radical pair kinetics in a magnetic field
journal, February 1997


Magnetic field effects in chemical kinetics and related phenomena
journal, January 1989

  • Steiner, Ulrich E.; Ulrich, Thomas
  • Chemical Reviews, Vol. 89, Issue 1
  • DOI: 10.1021/cr00091a003

Theory of chemically induced dynamic electron polarization. II
journal, September 1973

  • Pedersen, J. Boiden; Freed, Jack H.
  • The Journal of Chemical Physics, Vol. 59, Issue 6
  • DOI: 10.1063/1.1680418

Electron-Spin Polarizations Generated from Interactions between Excited Triplet Porphyrins and Stable Radicals Studied by Time-Resolved Electron Paramagnetic Resonance
journal, January 1997

  • Fujisawa, Jun-ichi; Ohba, Yasunori; Yamauchi, Seigo
  • The Journal of Physical Chemistry A, Vol. 101, Issue 4
  • DOI: 10.1021/jp9617433

Origin of nuclear spin polarization in triplet dimerizations
journal, March 1971

  • Closs, Gerhard L.
  • Journal of the American Chemical Society, Vol. 93, Issue 6
  • DOI: 10.1021/ja00735a064

Magnetic field dependent 13C and 1H CIDNP from biradicals. The role of the hyperfine coupling constant
journal, October 1978


The transient EPR spectra and spin dynamics of coupled three-spin systems in photosynthetic reaction centres
journal, January 1999

  • Salikhov, K. M.; van der Est, A. J.; Stehlik, D.
  • Applied Magnetic Resonance, Vol. 16, Issue 1
  • DOI: 10.1007/BF03161916

Linearly varying level model of CIDEP generated by intersystem crossings
journal, November 1994


A reassessment of the origin of photochemically induced dynamic nuclear polarization effects in solids
journal, November 2003


Light-induced triplet electron transfer in cyclohexene-bridged porphyrin–quinones detected by time-resolved electron paramagnetic resonance spectroscopy
journal, January 1993

  • Schlüpmann, Jenny; Lendzian, Friedhelm; Plato, Martin
  • J. Chem. Soc., Faraday Trans., Vol. 89, Issue 15
  • DOI: 10.1039/ft9938902853

Spin Dynamics of Radical Pairs with Restricted Geometries and Strong Exchange Coupling: The Role of Hyperfine Coupling
journal, June 2014

  • Zarea, Mehdi; Carmieli, Raanan; Ratner, Mark A.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 24
  • DOI: 10.1021/jp5039283

Theory of chemically induced magnetic polarization. Effects of ST ±1 mixing in strong magnetic fields
journal, September 1979

  • Adrian, F. J.; Monchick, L.
  • The Journal of Chemical Physics, Vol. 71, Issue 6
  • DOI: 10.1063/1.438616

Electron Spin Polarization Transfer from Photogenerated Spin-Correlated Radical Pairs to a Stable Radical Observer Spin
journal, June 2013

  • Colvin, Michael T.; Carmieli, Raanan; Miura, Tomoaki
  • The Journal of Physical Chemistry A, Vol. 117, Issue 25
  • DOI: 10.1021/jp4045012

Theory of chemically induced dynamic electron polarization. III. Initial triplet polarizations
journal, March 1975

  • Pedersen, J. Boiden; Freed, Jack H.
  • The Journal of Chemical Physics, Vol. 62, Issue 5
  • DOI: 10.1063/1.430695

Chemically induced dynamic electron polarization. II. A general theory for radicals produced by photochemical reactions of excited triplet carbonyl compounds
journal, February 1973

  • Wong, S. K.; Hutchinson, D. A.; Wan, J. K. S.
  • The Journal of Chemical Physics, Vol. 58, Issue 3
  • DOI: 10.1063/1.1679355

Magnetic-field effects on geminate radical-pair recombination
journal, January 1984

  • Weller, Albert; Staerk, Hubert; Treichel, Rainer
  • Faraday Discussions of the Chemical Society, Vol. 78
  • DOI: 10.1039/dc9847800271

The role of chemically-induced dynamic electron polarization (CIDEP) in chemistry
journal, January 1979

  • Hore, P. J.; Joslin, C. G.; McLauchlan, K. A.
  • Chemical Society Reviews, Vol. 8, Issue 1
  • DOI: 10.1039/cs9790800029

On the theory of chemically induced electron polarization (CIDEP): Vector model and an asymptotic solution
journal, May 1978

  • Monchick, L.; Adrian, F. J.
  • The Journal of Chemical Physics, Vol. 68, Issue 10
  • DOI: 10.1063/1.435507

Chemically induced dynamic electron polarization. Examples; of S-T±1 polarization
journal, May 1978


Transient nutation electron spin resonance spectroscopy on spin-correlated radical pairs: A theoretical analysis on hyperfine-induced nuclear modulations
journal, April 1997

  • Weber, Stefan; Kothe, Gerd; Norris, James R.
  • The Journal of Chemical Physics, Vol. 106, Issue 15
  • DOI: 10.1063/1.473617

Electron spin polarization in radical-triplet pairs. Size and dependence on diffusion
journal, December 1993

  • Goudsmit, Gert Hein; Paul, Henning; Shushin, Anatoly I.
  • The Journal of Physical Chemistry, Vol. 97, Issue 50
  • DOI: 10.1021/j100152a031

Electron spin polarization in a three-electron spin system. An application to bacterial photosynthesis
journal, June 1984


Detailed analysis of the mechanism of net electron spin polarization in liquid phase triplet-radical quenching
journal, November 1999