Nuclear spin ordering

The transformation of this molecular rotational order into nuclear spin order during the hydrogenation reaction leads to typical polarization patterns in the NMR spectra of the hydrogenation products. Depending on whether the experiment is performed inside or outside of a magnetic field (see Fig. 21.6), these types of experiments have been referred to under the acronyms PASADENA (Para-hydrogen and Synthesis Allow Dramatically Enhanced Nuclear Alignment) or... 

While all contributions to the spin Hamiltonian so far involve the electron spin and cause first-order energy shifts or splittings in the FPR spectmm, there are also tenns that involve only nuclear spms. Aside from their importance for the calculation of FNDOR spectra, these tenns may influence the FPR spectnim significantly in situations where the high-field approximation breaks down and second-order effects become important. The first of these interactions is the coupling of the nuclear spin to the external magnetic field, called the... 

In summary, for a homonuclear diatomic molecule there are generally (2/ + 1) (7+1) symmetric and (27+1)7 antisymmetric nuclear spin functions. For example, from Eqs. (50) and (51), the statistical weights of the symmetric and antisymmetric nuclear spin functions of Li2 will be and respectively. This is also true when one considers Li2 Li and Li2 Li. For the former, the statistical weights of the symmetric and antisymmetiic nuclear spin functions are and, respectively for the latter, they are and in the same order. 

An expansion in powers of 1 /c is a standard approach for deriving relativistic correction terms. Taking into account electron (s) and nuclear spins (1), and indicating explicitly an external electric potential by means of the field (F = —V0, or —— dAjdt if time dependent), an expansion up to order 1/c of the Dirac Hamiltonian including the... 

In order to describe nuclear spin-spin coupling, we need to include electron and nuclear spins, which are not present in the non-relativistic Hamilton operator. A relativistic treatment, as shown in Section 8.2, gives a direct nuclear-nuclear coupling term (eq. (8.33)). 

A completely different type of property is for example spin-spin coupling constants, which contain interactions of electronic and nuclear spins. One of the operators is a delta function (Fermi-Contact, eq. (10.78)), which measures the quality of the wave function at a single point, the nuclear position. Since Gaussian functions have an incorrect behaviour at the nucleus (zero derivative compared with the cusp displayed by an exponential function), this requires addition of a number of very tight functions (large exponents) in order to predict coupling constants accurately. ... 

The origin of postulate (iii) lies in the electron-nuclear hyperfine interaction. If the energy separation between the T and S states of the radical pair is of the same order of magnitude as then the hyperfine interaction can represent a driving force for T-S mixing and this depends on the nuclear spin state. Only a relatively small preference for one spin-state compared with the other is necessary in the T-S mixing process in order to overcome the Boltzmann polarization (1 in 10 ). The effect is to make n.m.r. spectroscopy a much more sensitive technique in systems displaying CIDNP than in systems where only Boltzmann distributions of nuclear spin states obtain. More detailed consideration of postulate (iii) is deferred until Section II,D. 

It can also be seen from Fig. 6 that if the T+x or T x states mixed with S, this would involve concomitant electron and nuclear spin flipping in order that the total spin angular momentum be conserved, and this would ultimately produce the same polarization in c- and e-products. This point will be discussed further in Section IV. 

Furthermore, even though the time dependence of the mixing process has been placed in Jee> ee must approximately equal Uj dming successive encounters in order that the time development of nuclear spin states in... 

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. 

Magnetic dipole interaction Hm (4.47) and electric quadmpole interaction //q (4.29) both depend on the magnetic quantum numbers of the nuclear spin. Therefore, their combined Hamiltonian may be difficult to evaluate. There are closed-form solutions of the problem [64], but relatively simple expressions exist only for a few special cases [65]. In Sect. 4.5.1 it will be shown which kind of information can be obtained from a perturbation treatment if one interaction of the two is much weaker than the other and will be shown below. In general, however, if the interactions are of the same order of magnitude, eQV Jl, and... 

NMR spectroscopy is a powerful technique to study molecular structure, order, and dynamics. Because of the anisotropy of the interactions of nuclear spins with each other and with their environment via dipolar, chemical shift, and quadrupolar interactions, the NMR frequencies depend on the orientation of a given molecular unit relative to the external magnetic field. NMR spectroscopy is thus quite valuable to characterize partially oriented systems. Solid-state NMR... 

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