Nuclear spin systems, theory

We now come back to the simplest possible nuclear spin system, containing only one kind of nuclei 7, hyperfine-coupled to electron spin S. In the Solomon-Bloembergen-Morgan theory, both spins constitute the spin system with the unperturbed Hamiltonian containing the two Zeeman interactions. The dipole-dipole interaction and the interactions leading to the electron spin relaxation constitute the perturbation, treated by means of the Redfield theory. In this section, we deal with a situation where the electron spin is allowed to be so strongly coupled to the other degrees of freedom that the Redfield treatment of the combined IS spin system is not possible. In Section V, we will be faced with a situation where the electron spin is in... 

Relaxation theory of nuclear spin systems is well documented in several books18-24 and review articles.4-25-26 Therefore, the theory presented in this chapter is limited to a summary of some of the basic concepts crucial for understanding the material in the following sections. Furthermore, the discussion will be focused on dipolar relaxation, which is known to be the dominant relaxation mechanism in most molecules of chemical interest. For a detailed treatment of other mechanisms, the reader is referred to appropriate review articles.4-18"26... 

The theory describing nuclear spin systems in a strong external magnetic field and subjected to RF irradiation has been thoroughly treated in the literature (for instance, see refs 3,5-8). The following section presents nothing new in this respect rather it is meant to provide a brief introduction of the basic concepts, definitions and notation used throughout this chapter. 

The contributions of the second order terms in for the splitting in ESR is usually neglected since they are very small, and in feet they correspond to the NMR lines detected in some ESR experiments (5). However, the analysis of the second order expressions is important since it allows for the calculation of the indirect nuclear spin-spin couplings in NMR spectroscoi. These spin-spin couplings are usually calcdated via a closed shell polarization propagator (138-140), so that, the approach described here would allow for the same calculations to be performed within the electron Hopagator theory for open shell systems. 

Another possibility to introduce a semiclasscial initial value representation for the spin-coherent state propagator is to exploit the close relation between Schwinger s representation of a spin system and the spin-coherent state theory [100, 133-135]. To illustrate this approach, we consider an electronic two-level system coupled to Vvib nuclear DoF. Within the mapping approach the semiclassical propagator for this system is given by... 

A systematic development of relativistic molecular Hamiltonians and various non-relativistic approximations are presented. Our starting point is the Dirac one-fermion Hamiltonian in the presence of an external electromagnetic field. The problems associated with generalizing Dirac s one-fermion theory smoothly to more than one fermion are discussed. The description of many-fermion systems within the framework of quantum electrodynamics (QED) will lead to Hamiltonians which do not suffer from the problems associated with the direct extension of Dirac s one-fermion theory to many-fermion system. An exhaustive discussion of the recent QED developments in the relevant area is not presented, except for cursory remarks for completeness. The non-relativistic form (NRF) of the many-electron relativistic Hamiltonian is developed as the working Hamiltonian. It is used to extract operators for the observables, which represent the response of a molecule to an external electromagnetic radiation field. In this study, our focus is mainly on the operators which eventually were used to calculate the nuclear magnetic resonance (NMR) chemical shifts and indirect nuclear spin-spin coupling constants. 

In an alternative formulation of the Redfield theory, one expresses the density operator by expansion in a suitable operator basis set and formulates the equation of motion directly in terms of the expectation values of the operators (18,20,50). Consider a system of two nuclear spins with the spin quantum number of 1/2,1, and N, interacting with each other through the scalar J-coupling and dipolar interaction. In an isotropic liquid, the former interaction gives rise to J-split doublets, while the dipolar interaction acts as a relaxation mechanism. For the discussion of such a system, the appropriate sixteen-dimensional basis set can for example consist of the unit operator, E, the operators corresponding to the Cartesian components of the two spins, Ix, ly, Iz, Nx, Ny, Nz and the products of the components of I and the components of N (49). These sixteen operators span the Liouville space for our two-spin system. If we concentrate on the longitudinal relaxation (the relaxation connected to the distribution of populations), the Redfield theory predicts the relaxation to follow a set of three coupled differential equations ... 

The basic idea of the slow-motion theory is to treat the electron spin as a part of the lattice and limit the spin part of the problem to the nuclear spin rather than the IS system. The difficult part of the problem is to treat, in an appropriate way, the combined lattice, now containing the classical degrees of freedom (such as rotation in condensed matter) as well as quantized degrees of freedom (such as the electron Zeeman interaction). The Liouville superoperator formalism is very well suited for treating this type of problems. 

Assuming that the lattice can, on the time scale relevant for the evolution of the nuclear spin density operator, be considered to remain in thermal equilibrium, a = a, and applying the Redfield theory to the nuclear spin sub-system allows us to obtain the following expressions for nuclear spin-lattice and spin spin relaxation rates ... 

The theory of nuclear spin relaxation (see monographs by Slichter [4], Abragam [5] and McConnell [6] for comprehensive presentations) is usually formulated in terms of the evolution of the density operator, cr, for the spin system under consideration from some kind of a non-equilibrium state, created normally by one or more radio-frequency pulses, to thermal equilibrium, described by Using the Bloch-Wangsness-Redfield (BWR) theory, usually appropriate for the liquid state, we can write [7, 8] ... 

In the discussion to follow certain aspects of chemical shifts and nuclear spin-spin interactions will be reviewed. However, it is not our intention to give the theories of these effects with any degree of completeness since excellent treatments may be found in reviews and the original literature 108). We only hope here to point out some results and approaches of NMR particularly applicable to inorganic systems. Let it suffice at this point to say that chemical shifts of nuclei arise from shielding effects of nearby electrons. The field Hm seen by the nucleus is not the externally applied field 770, but... 

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