Theory Zeeman Hamiltonian

We calculate the effects of the Hamiltonian (8.105) on these zeroth-order states using perturbation theory. This is exactly the same procedure as that which we used to construct the effective Hamiltonian in chapter 7. Our objective here is to formulate the terms in the effective Hamiltonian which describe the nuclear spin-rotation interaction and the susceptibility and chemical shift terms in the Zeeman Hamiltonian. We deal with them in much more detail at this point so that we can interpret the measurements on closed shell molecules by molecular beam magnetic resonance. The first-order corrections of the perturbation Hamiltonian are readily calculated to be... 

Radford (1961, 1962) and Radford and Broida (1962) presented a complete theory of the Zeeman effect for diatomic molecules that included perturbation effects. This led to a series of detailed investigations of the CN B2E+ (v — 0) A2II (v = 10) perturbation in which many of the techniques of modern high-resolution molecular spectroscopy and analysis were first demonstrated anticrossing spectroscopy (Radford and Broida, 1962, 1963), microwave optical double resonance (Evenson, et at, 1964), excited-state hyperfine structure with perturbations (Radford, 1964), effect of perturbations on radiative lifetimes and on inter-electronic-state collisional energy transfer (Radford and Broida, 1963). A similarly complete treatment of the effect of a magnetic field on the CO a,3E+ A1 perturbation complex is reported by Sykora and Vidal (1998). The AS = 0 selection rule for the Zeeman Hamiltonian leads to important differences between the CN B2E+ A2II and CO a/3E+ A1 perturbation plus Zeeman examples, primarily in the absence in the latter case of interference effects between the Zeeman and intramolecular perturbation terms. 

The High-Field Approximation In most NMR experiments the nuclear Zeeman interaction with the static external magnetic field is much stronger than all other interactions of the nuclear spins. As a result of these differences in the size, it is usually possible to treat these interactions in first order perturbation theory, i.e. use only those terms which commute with the Zeeman Hamiltonian, the so called secular terms. This approximation is called the high field approximation. While the single particle interactions like CSA or quadrupolar interaction have a unique form, for bilinear interactions, one has to distinguish between a homonuclear and a hetero-nuclear case. The secular parts of Hamiltonians discussed in the previous section are collected in Table 1. 

Weak quadrupole perturbation of magnetic levels In this case the quadrupole interaction operator (18.51) must be projected onto the coordinate system associated with the magnetic (Zeeman) hamiltonian (18.1). Since the former is actually a tensor operator, the projection introduces a more complicated angular dependence than in the converse case considered in section 1.3.2.2. The energy levels become, on the basis of first-order perturbation 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... 

Bertini and co-workers 119) and Kruk et al. 96) formulated a theory of electron spin relaxation in slowly-rotating systems valid for arbitrary relation between the static ZFS and the Zeeman interaction. The unperturbed, static Hamiltonian was allowed to contain both these interactions. Such an unperturbed Hamiltonian, Hq, depends on the relative orientation of the molecule-fixed P frame and the laboratory frame. For cylindrically symmetric ZFS, we need only one angle, p, to specify the orientation of the two frames. The eigenstates of Hq(P) were used to define the basis set in which the relaxation superoperator Rzpsi ) expressed. The superoperator M, the projection vectors and the electron-spin spectral densities cf. Eqs. (62-64)), all become dependent on the angle p. The expression in Eq. (61) needs to be modified in two ways first, we need to include the crossterms electron-spin spectral densities, and These terms can be... 

A more general theory for outer-sphere paramagnetic relaxation enhancement, valid for an arbitrary relation between the Zeeman coupling and the axial static ZFS, has been developed by Kruk and co-workers (96 in the same paper which dealt with the inner-sphere case. The static ZFS was included, along with the Zeeman interaction in the unperturbed Hamiltonian. The general expression for the nuclear spin-lattice relaxation rate of the outer-sphere nuclei was written in terms of electron spin spectral densities, as ... 

We cannot obtain simple analytic solutions for as a function of 6 and cp that are completely general. Using perturbation theory, we can, however, obtain solutions when the Zeeman interaction is much greater than D. To illustrate how this is accomplished, we shall find the solution for axial symmetry when the spin Hamiltonian is... 

Abstract. Following a suggestion of Kostelecky et al. we have evaluated a test of CPT and Lorentz invariance from the microwave spectrosopy of muonium. Precise measurements have been reported for the transition frequencies U12 and 1/34 for ground state muonium in a magnetic field H of 1.7 T, both of which involve principally muon spin flip. These frequencies depend on both the hyperfine interaction and Zeeman effect. Hamiltonian terms beyond the standard model which violate CPT and Lorentz invariance would contribute shifts <5 12 and <5 34. The nonstandard theory indicates that P12 and 34 should oscillate with the earth s sidereal frequency and that 5v 2 and <5 34 would be anticorrelated. We find no time dependence in m2 — vza at the level of 20 Hz, which is used to set an upper limit on the size of CPT and Lorentz violating parameters. 

The effective Hamiltonian used by Saykally, Evenson, Comben and Brown [62] contains terms which we have already met in this chapter, and which we will therefore deal with fairly briefly, with appropriate references to the details given elsewhere, particularly in this section. The theory has been developed in a number of papers, particularly by Brown, Kopp, Malmberg and Rydh [63], Brown and Merer [64], who dealt with n states of triplet and higher spin multiplicity, and Steimle and Brown [65] who specifically addressed the theory of the A-doubling of CO in the 3 n state. The theory of the Zeeman interactions follows closely that developed to analyse the magnetic resonance spectra of OH by Brown, Raise, Kerr and Milton [66]. All of these... 

We are interested in what happens when a magnetic moment fJt interacts with an applied magnetic field B0—an interaction commonly called the Zeeman interaction. Classically, the energy of this system varies, as illustrated in Fig. 2.1a, with the cosine of the angle between l and B0, with the lowest energy when they are aligned. In quantum theory, the Zeeman appears in the Hamiltonian operator... 

We now calculate the perturbation to the Zeeman field due to the quadrupolar interaction by means of average Hamiltonian theory.This is accomplished by transforming TYq to the Zeeman interaction frame and then applying the spherical tensor rotation properties to the spin elements 72,The resulting quadrupolar Hamiltonian TTq in the rotating frame is given by ... 

The interpretation of a complex Mossbauer spectrum will obviously be simplified if the relative intensities of the various components are known. Once the energy levels of the Zeeman/quadrupole Hamiltonian have been calculated, and the spin quantum numbers for each state assigned (or appropriate linear combinations if the states are mixed), it is possible to calculate the intensities from the theory of the coupling of two angular momentum states [32, 33]. 

For the simulation of ESR spectra one has to solve the spin Hamiltonian of Eq. (10). The easiest way to do this is to regard all the different terms in the spin Hamiltonian as small compared with the electron Zeeman interaction and to use perturbation theory of the first order. The Zeeman term can easily be solved within the eigensystem of the Sz operator (in the main axis system of the g-tensor or S 2=5 for isotropic cases), for instance in the isotropic case ... 

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