Magnetic field effects in chemical systems
Magnetic fields influence the rate and/or yield of chemical reactions that proceed via spin correlated radical pair intermediates. The field of spin chemistry centres around the study of such magnetic field effects (MFEs). This thesis is particularly concerned with the effects of the weak magnetic f...
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| Format: | Thesis |
| Language: | English |
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2007
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| _version_ | 1797104137606791168 |
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| author | Rodgers, C Dr Christopher T. Rodgers |
| author2 | Hore, P |
| author_facet | Hore, P Rodgers, C Dr Christopher T. Rodgers |
| author_sort | Rodgers, C |
| collection | OXFORD |
| description | Magnetic fields influence the rate and/or yield of chemical reactions that proceed via spin correlated radical pair intermediates. The field of spin chemistry centres around the study of such magnetic field effects (MFEs). This thesis is particularly concerned with the effects of the weak magnetic fields B₀ ~ 1mT relevant in the ongoing debates on the mechanism by which animals sense the geomagnetic field and on the putative health effects of environmental electromagnetic fields. Relatively few previous studies have dealt with such weak magnetic fields. This thesis presents several new theoretical tools and applies them to interpret experimental measurements. Chapter 1 surveys the development and theory of spin chemistry. Chapter 2 introduces the use of Tikhonov and Maximum Entropy Regularisation methods as a new means of analysing MARY field effect data. These are applied to recover details of the diffusive motion of reacting pyrene and N,N-dimethylaniline radicals. Chapter 3 gives a fresh derivation and appraisal of an approximate, semiclassical approach to MFEs. Monte Carlo calculations allow the elucidation of several "rules of thumb" for interpreting MFE data. Chapter 4 discusses recent optically-detected zero-field EPR measurements, adapting the gamma-COMPUTE algorithm from solid state NMR for their interpretation. Chapter 5 explores the role of RF polarisation in producing MFEs. The breakdown in weak fields of the familiar rotating frame approximation is analysed. Chapter 6 reviews current knowledge and landmark experiments in the area of animal magnetoreception. The origins of the sensitivity of European robins Erithacus rubecula to the Earth’s magnetic field are given particular attention. In Chapter 7, Schulten and Ritz’s hypothesis that avian magnetoreception is founded on a radical pair mechanism (RPM) reaction is appraised through calculations in model systems. Chapter 8 introduces quantitative methods of analysing anisotropic magnetic field effects using spherical harmonics. Chapter 9 considers recent observations that European robins may sometimes be disoriented by minuscule RF fields. These are shown to be consistent with magnetoreception via a radical pair with no (effective) magnetic nuclei in one of the radicals. |
| first_indexed | 2024-03-07T06:29:36Z |
| format | Thesis |
| id | oxford-uuid:f5878b88-c5ba-4cbd-83af-857431aef66e |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T06:29:36Z |
| publishDate | 2007 |
| record_format | dspace |
| spelling | oxford-uuid:f5878b88-c5ba-4cbd-83af-857431aef66e2022-03-27T12:27:56ZMagnetic field effects in chemical systemsThesishttp://purl.org/coar/resource_type/c_db06uuid:f5878b88-c5ba-4cbd-83af-857431aef66ePhotochemistry and reaction dynamicsMolecular biophysics (biochemistry)Spectroscopy and molecular structureBehaviour (zoology)Theoretical chemistryBiophysical chemistryPhysical SciencesChemistry & allied sciencesNMR spectroscopyPhysical & theoretical chemistryBiophysicsEnglishOxford University Research Archive - Valet2007Rodgers, CDr Christopher T. RodgersHore, PTimmel, CMagnetic fields influence the rate and/or yield of chemical reactions that proceed via spin correlated radical pair intermediates. The field of spin chemistry centres around the study of such magnetic field effects (MFEs). This thesis is particularly concerned with the effects of the weak magnetic fields B₀ ~ 1mT relevant in the ongoing debates on the mechanism by which animals sense the geomagnetic field and on the putative health effects of environmental electromagnetic fields. Relatively few previous studies have dealt with such weak magnetic fields. This thesis presents several new theoretical tools and applies them to interpret experimental measurements. Chapter 1 surveys the development and theory of spin chemistry. Chapter 2 introduces the use of Tikhonov and Maximum Entropy Regularisation methods as a new means of analysing MARY field effect data. These are applied to recover details of the diffusive motion of reacting pyrene and N,N-dimethylaniline radicals. Chapter 3 gives a fresh derivation and appraisal of an approximate, semiclassical approach to MFEs. Monte Carlo calculations allow the elucidation of several "rules of thumb" for interpreting MFE data. Chapter 4 discusses recent optically-detected zero-field EPR measurements, adapting the gamma-COMPUTE algorithm from solid state NMR for their interpretation. Chapter 5 explores the role of RF polarisation in producing MFEs. The breakdown in weak fields of the familiar rotating frame approximation is analysed. Chapter 6 reviews current knowledge and landmark experiments in the area of animal magnetoreception. The origins of the sensitivity of European robins Erithacus rubecula to the Earth’s magnetic field are given particular attention. In Chapter 7, Schulten and Ritz’s hypothesis that avian magnetoreception is founded on a radical pair mechanism (RPM) reaction is appraised through calculations in model systems. Chapter 8 introduces quantitative methods of analysing anisotropic magnetic field effects using spherical harmonics. Chapter 9 considers recent observations that European robins may sometimes be disoriented by minuscule RF fields. These are shown to be consistent with magnetoreception via a radical pair with no (effective) magnetic nuclei in one of the radicals. |
| spellingShingle | Photochemistry and reaction dynamics Molecular biophysics (biochemistry) Spectroscopy and molecular structure Behaviour (zoology) Theoretical chemistry Biophysical chemistry Physical Sciences Chemistry & allied sciences NMR spectroscopy Physical & theoretical chemistry Biophysics Rodgers, C Dr Christopher T. Rodgers Magnetic field effects in chemical systems |
| title | Magnetic field effects in chemical systems |
| title_full | Magnetic field effects in chemical systems |
| title_fullStr | Magnetic field effects in chemical systems |
| title_full_unstemmed | Magnetic field effects in chemical systems |
| title_short | Magnetic field effects in chemical systems |
| title_sort | magnetic field effects in chemical systems |
| topic | Photochemistry and reaction dynamics Molecular biophysics (biochemistry) Spectroscopy and molecular structure Behaviour (zoology) Theoretical chemistry Biophysical chemistry Physical Sciences Chemistry & allied sciences NMR spectroscopy Physical & theoretical chemistry Biophysics |
| work_keys_str_mv | AT rodgersc magneticfieldeffectsinchemicalsystems AT drchristophertrodgers magneticfieldeffectsinchemicalsystems |