Magnetic resonance techniques, including NMR and EPR, are extremely powerful tools for investigating the structure and dynamics of molecules. 

This module offers the student the opportunity to study the underlying physical principles of NMR and EPR, primarily in the solid state, and the surrounding magnetic interactions that determine the appearance of the experimental spectra. 

Coverage of conventional principles in magnetic resonance, showing how the resonance frequency of a nucleus (or electron) is affected not only by the applied field but also by the electronic environment and surrounding nuclei, will be presented to the students.

A more advanced EPR technique, called ENDOR, where EPR and NMR transitions are simultaneously pumped and then monitored, will also be introduced in both liquid phase and solid phase conditions. 

Particular emphasis will be devoted to the analysis of NMR and EPR spectra in the solid state. 

The anisotropic interactions responsible for the broad and more complex spectral line shapes experienced in the solid state (compared to the isotropic profiles experienced in the liquid state) will be treated using a series of examples. 

The advanced methodology of angular selective ENDOR, used to analyse and extract structural information for paramagnetic species in frozen solution, will also be covered. 

• Understand the origin of the Zeeman interaction; 

• Understand the importance of spin angular momentum and the spin magnetic moment in magnetic resonance spectroscopy; 

• Describe the behaviour of nuclear and electron spins in an applied magnetic field; 

• Understand the role of spin angular momentum as the foundation in NMR and EPR; 

• Describe the importance of various magnetic interactions, such as spin-spin coupling, as a vital source of information;  

• Understand the nature of anisotropic interactions in the solid state, and how they dictate the shape of the spectra; 

• Understand how various magnetic interactions including electron Zeeman interactions, zero field splitting, hyperfine interactions, nuclear Zeeman interactions, and quadrupole interactions, can be extracted from the EPR spectrum; 

• Know how dynamic, as well as structural information can be accessed in the solid state, and understand the importance of the timeframe of the NMR techniques in dynamic studies; 

• Discuss the approaches taken to record NMR spectra in solid state; 

• Describe how the ENDOR technique is performed and the role of saturation and relaxation phenomena in acquiring ENDOR signals with optimal amplitudes; 

• Describe how the angular selective ENDOR methodology is applied to study paramagnetic systems in the solid state.

A blend of on-line learning activities with face-to-face small group learning support and feedback.

The module will be delivered in 10 two-hour lectures, supplemented by 4 one-hour class tutorials. 

Chemistry-Specific Skills:

• Link formal equations to observed NMR/EPR spectra; 

• Interpret experimental observations in terms of the molecular and structural properties of the system; 

• Select appropriate techniques for determination of structure in solution or solid state for a range of chemical situations; 

• Assess the advantages/disadvantages of the different techniques for each particular purpose and chemical problem; 

• Appreciate the steps involved in the analysis of modern magnetic resonance experiments; 

• Understand how NMR/EPR may be used to study problems of general chemical interest; 

• Use qualitative arguments to develop a theoretical description of magnetic resonance phenomena; 

• Use quantitative measurements to verify or disprove theoretical models. 

Employability skills:      

This module is delivered and aligns with the following University Graduate Attributes: 

• Contribute to discussions, negotiate, and present with impact.  

• Consider own personal and professional ethical, social, and environmental responsibilities.  

• Demonstrate personal and professional integrity, reliability, and competence.  

• Be mindful of the Climate Emergency and the UN's Sustainable Development Goals  

• Identify, define, and analyse complex issues and ideas, exercising critical judgment in evaluating sources of information.  

• Demonstrate intellectual curiosity and engage in the pursuit of new knowledge and understanding. 

• Investigate problems and offer effective solutions, reflecting on and learning from successes and failures.  

• Generate original ideas and apply creative, imaginative, and innovative thinking in response to identified needs and problems.  

• Actively reflect on own studies achievements and self-identity  

• Demonstrate resilience, adaptability, and creativity in dealing with challenges, and be open to change.  

• Identify and articulate own skills, knowledge and understanding confidently and in a variety of contexts.  

• Engage with new ideas, opportunities, and technologies, building knowledge and experience to make informed decisions about own future. 

Graduate Attributes – Assessment:    

 Written Assessment                 20% 

• Contribute to discussions, negotiate, and present with impact.  

• Consider own personal and professional ethical, social, and environmental responsibilities.  

• Demonstrate personal and professional integrity, reliability, and competence.  

• Be mindful of the Climate Emergency and the UN's Sustainable Development Goals  

• Identify, define, and analyse complex issues and ideas, exercising critical judgment in evaluating sources of information.  

• Demonstrate intellectual curiosity and engage in the pursuit of new knowledge and understanding. 

• Investigate problems and offer effective solutions, reflecting on and learning from successes and failures.  

• Generate original ideas and apply creative, imaginative, and innovative thinking in response to identified needs and problems.  

• Actively reflect on own studies achievements and self-identity  

• Demonstrate resilience, adaptability, and creativity in dealing with challenges, and be open to change.  

• Identify and articulate own skills, knowledge and understanding confidently and in a variety of contexts.  

• Engage with new ideas, opportunities, and technologies, building knowledge and experience to make informed decisions about own future. 

 Exam                                        80% 

• Contribute to discussions, negotiate, and present with impact.  

• Consider own personal and professional ethical, social, and environmental responsibilities.  

• Demonstrate personal and professional integrity, reliability, and competence.  

• Be mindful of the Climate Emergency and the UN's Sustainable Development Goals  

• Identify, define, and analyse complex issues and ideas, exercising critical judgment in evaluating sources of information.  

• Demonstrate intellectual curiosity and engage in the pursuit of new knowledge and understanding. 

• Investigate problems and offer effective solutions, reflecting on and learning from successes and failures.  

• Generate original ideas and apply creative, imaginative, and innovative thinking in response to identified needs and problems.  

• Actively reflect on own studies achievements and self-identity  

• Demonstrate resilience, adaptability, and creativity in dealing with challenges, and be open to change.  

• Identify and articulate own skills, knowledge and understanding confidently and in a variety of contexts.  

• Engage with new ideas, opportunities, and technologies, building knowledge and experience to make informed decisions about own future. 

Sustainable Development Goals:    

This module does not align with any of the Sustainable Development Goals, but its applications will contribute towards all in part.

The module will be assessed by a combination of coursework (20%) and written examination (80%). 

The single assessed piece of open-book coursework, containing questions based on both the NMR and EPR components of the module, will be delivered during the course.

Foundations in Solid State NMR: This part of the course will provide an introduction to solid-state NMR spectroscopy, focusing initially on relevant theoretical background and experimental techniques. 

The discussion of background theory will highlight the significant differences between solid-state NMR and liquid-state NMR, focusing on the main anisotropic NMR interactions that are important in the solid state. 

The discussion of experimental strategies will then focus on the techniques for recording:  

a) broad-line solid-state NMR spectra (in which the anisotropic NMR interactions are studied), 

b) high-resolution solid-state NMR spectra (in which the aim is to record narrow-line spectra that resemble those recorded in liquid-state NMR). 

The course will then build upon these foundations by discussing the applications of solid-state NMR to investigate structural and dynamic properties of solids, highlighting the scope and limitations of different types of solid-state NMR technique. 

Several recent examples of the application of solid-state NMR to solve problems in solid-state and materials chemistry will be presented. 

Students attending the course will emerge with an appreciation of the types of problem that can be tackled successfully by solid-state NMR, and the particular NMR technique (or combination of techniques) is most suitable for investigating each type of problem.

Foundations of liquid and solid state EPR & ENDOR: The basic principles underlying the EPR technique will be covered, including coverage of the form of the spin Hamiltonian for systems in the solid state. This will initially be treated for the liquid phase, before considering the more complex case of the solid-state Anisotropy

Anisotropy of the g and A hyperfine tensors, and the role of symmetry as manifested in the g/A frame will then be presented to the students. 

The theory and applications of angular selective ENDOR, based on the angular dependency of the EPR spectra, will also be covered in the lectures. Examination of the profiles of EPR spectra in the solid state will then be covered. 

The lectures will then cover the theory of ENDOR, with particular emphasis on the saturation and relaxation pathways important in this technique. 

The role of angular selection as a means of determining structural information for paramagnetic centres in the solid state will then be given. 

Examples of systems with low g anisotropy (no hyperfine interaction) leading to powder ENDOR patterns, and subsequently axial g anisotropy and axial hyperfine, leading so ‘single crystal-like’ ENDOR patterns will then be investigated. 

The students will then appreciate the experimental approaches taken to obtain EPR and ENDOR spectra of paramagnetic centres in the solid state (primarily in frozen solution) and the general methodologies subsequently involved in the analysis and understanding of the experimental data. 

Numerous examples of how to interpret solid state EPR / ENDOR spectra will be covered during the course.