ANALYSIS OF ANISOTROPIC ELECTRON-SPIN POLARIZATION IN THE PHOTOSYNTHETIC BACTERIUM RHODOSPIRILLUM-RUBRUM - EVIDENCE THAT THE SIGN OF THE EXCHANGE INTERACTION IN THE PRIMARY RADICAL PAIR IS POSITIVE

The transient electron paramagnetic resonance spectrum of pre-reduced, perdeuterated cells of the photosynthetic bacterium Rhodospirillum rubrum is analysed using a quantum mechanical description of the spin dynamics. The spectrum, of the reduced secondary electron acceptor (a ubisemiquinone anion,...

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Main Authors: Hore, P, Riley, D, Semlyen, J, Zwanenburg, G, Hoff, A
Format: Journal article
Language:English
Published: 1993
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author Hore, P
Riley, D
Semlyen, J
Zwanenburg, G
Hoff, A
author_facet Hore, P
Riley, D
Semlyen, J
Zwanenburg, G
Hoff, A
author_sort Hore, P
collection OXFORD
description The transient electron paramagnetic resonance spectrum of pre-reduced, perdeuterated cells of the photosynthetic bacterium Rhodospirillum rubrum is analysed using a quantum mechanical description of the spin dynamics. The spectrum, of the reduced secondary electron acceptor (a ubisemiquinone anion, Q-), displays anisotropic electron spin polarization, which is seen to arise principally from a combination of three interactions: the dipolar coupling of Q- to the reduced primary electron acceptor (a bacteriopheophytin anion, I-), the g-tensor anisotropy of Q- and the electronic exchange interaction between I- and the oxidised form of the primary electron donor (a bacteriochlorophyll dimer cation, P+). Using parameter values for Rhodobacter sphaeroides, it emerges that the P+I- exchange interaction JPI must be positive to account for the phase of the polarization, that is, the singlet state of the primary radical pair P+I- must lie higher in energy than the triplet. This finding puts restrictions on the permissible values of the energy gap between P* (the excited singlet state of P) and P+BA- (where BA is the accessory chlorophyll) and gives information on the mechanism of primary charge separation, P*I → P+I-.
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spelling oxford-uuid:d1ab5497-d069-4708-916e-d87db7d00f9d2022-03-27T07:58:32ZANALYSIS OF ANISOTROPIC ELECTRON-SPIN POLARIZATION IN THE PHOTOSYNTHETIC BACTERIUM RHODOSPIRILLUM-RUBRUM - EVIDENCE THAT THE SIGN OF THE EXCHANGE INTERACTION IN THE PRIMARY RADICAL PAIR IS POSITIVEJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:d1ab5497-d069-4708-916e-d87db7d00f9dEnglishSymplectic Elements at Oxford1993Hore, PRiley, DSemlyen, JZwanenburg, GHoff, AThe transient electron paramagnetic resonance spectrum of pre-reduced, perdeuterated cells of the photosynthetic bacterium Rhodospirillum rubrum is analysed using a quantum mechanical description of the spin dynamics. The spectrum, of the reduced secondary electron acceptor (a ubisemiquinone anion, Q-), displays anisotropic electron spin polarization, which is seen to arise principally from a combination of three interactions: the dipolar coupling of Q- to the reduced primary electron acceptor (a bacteriopheophytin anion, I-), the g-tensor anisotropy of Q- and the electronic exchange interaction between I- and the oxidised form of the primary electron donor (a bacteriochlorophyll dimer cation, P+). Using parameter values for Rhodobacter sphaeroides, it emerges that the P+I- exchange interaction JPI must be positive to account for the phase of the polarization, that is, the singlet state of the primary radical pair P+I- must lie higher in energy than the triplet. This finding puts restrictions on the permissible values of the energy gap between P* (the excited singlet state of P) and P+BA- (where BA is the accessory chlorophyll) and gives information on the mechanism of primary charge separation, P*I → P+I-.
spellingShingle Hore, P
Riley, D
Semlyen, J
Zwanenburg, G
Hoff, A
ANALYSIS OF ANISOTROPIC ELECTRON-SPIN POLARIZATION IN THE PHOTOSYNTHETIC BACTERIUM RHODOSPIRILLUM-RUBRUM - EVIDENCE THAT THE SIGN OF THE EXCHANGE INTERACTION IN THE PRIMARY RADICAL PAIR IS POSITIVE
title ANALYSIS OF ANISOTROPIC ELECTRON-SPIN POLARIZATION IN THE PHOTOSYNTHETIC BACTERIUM RHODOSPIRILLUM-RUBRUM - EVIDENCE THAT THE SIGN OF THE EXCHANGE INTERACTION IN THE PRIMARY RADICAL PAIR IS POSITIVE
title_full ANALYSIS OF ANISOTROPIC ELECTRON-SPIN POLARIZATION IN THE PHOTOSYNTHETIC BACTERIUM RHODOSPIRILLUM-RUBRUM - EVIDENCE THAT THE SIGN OF THE EXCHANGE INTERACTION IN THE PRIMARY RADICAL PAIR IS POSITIVE
title_fullStr ANALYSIS OF ANISOTROPIC ELECTRON-SPIN POLARIZATION IN THE PHOTOSYNTHETIC BACTERIUM RHODOSPIRILLUM-RUBRUM - EVIDENCE THAT THE SIGN OF THE EXCHANGE INTERACTION IN THE PRIMARY RADICAL PAIR IS POSITIVE
title_full_unstemmed ANALYSIS OF ANISOTROPIC ELECTRON-SPIN POLARIZATION IN THE PHOTOSYNTHETIC BACTERIUM RHODOSPIRILLUM-RUBRUM - EVIDENCE THAT THE SIGN OF THE EXCHANGE INTERACTION IN THE PRIMARY RADICAL PAIR IS POSITIVE
title_short ANALYSIS OF ANISOTROPIC ELECTRON-SPIN POLARIZATION IN THE PHOTOSYNTHETIC BACTERIUM RHODOSPIRILLUM-RUBRUM - EVIDENCE THAT THE SIGN OF THE EXCHANGE INTERACTION IN THE PRIMARY RADICAL PAIR IS POSITIVE
title_sort analysis of anisotropic electron spin polarization in the photosynthetic bacterium rhodospirillum rubrum evidence that the sign of the exchange interaction in the primary radical pair is positive
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AT rileyd analysisofanisotropicelectronspinpolarizationinthephotosyntheticbacteriumrhodospirillumrubrumevidencethatthesignoftheexchangeinteractionintheprimaryradicalpairispositive
AT semlyenj analysisofanisotropicelectronspinpolarizationinthephotosyntheticbacteriumrhodospirillumrubrumevidencethatthesignoftheexchangeinteractionintheprimaryradicalpairispositive
AT zwanenburgg analysisofanisotropicelectronspinpolarizationinthephotosyntheticbacteriumrhodospirillumrubrumevidencethatthesignoftheexchangeinteractionintheprimaryradicalpairispositive
AT hoffa analysisofanisotropicelectronspinpolarizationinthephotosyntheticbacteriumrhodospirillumrubrumevidencethatthesignoftheexchangeinteractionintheprimaryradicalpairispositive