Matrix elements of the quadrupole Hamiltonian

In both of the above treatments, spherical tensor and cartesian, we have factored the quadrupole interaction into the product of two terms, one of which operates only on functions of proton coordinates within the nucleus and the other only on functions of coordinates of electrons and protons outside the nucleus. We shall see in subsequent chapters that the spherical tensor form is rather more convenient for the calculation of matrix elements of 3Cq. However, we shall find this easier to appreciate once we have considered some of the theory of angular momentum in chapter 5 so we defer discussion until later. 

Both equations (4.30) and (4.37) are rather inconvenient for our purposes since their explicit evaluation demands that we treat the nucleus as a many particle system. In fact, these forms would allow us to treat problems of greater complexity than those encountered in molecular spectroscopy. In general, we shall only be concerned with the nucleus in its ground state, and it is only necessary to characterise the nuclear 

The matrix elements which arise in molecular spectroscopy are always diagonal in I, but may be off-diagonal in Mj. It can be shown that the operator 

Hence the nuclear quadrupole tensor components are given by 

We will return to the quadrupole interaction in following chapters, but we now re-examine the general expansion of the electrostatic interaction and, in particular, the possibility of other nuclear electrostatic multipole moments. Because our multipole expansion is performed in a coordinate system with origin at the centre of charge of the protons p in the nucleus, the nuclear electric dipole moment is zero. However, this result arises only from our choice of origin and we now show that there are much 

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Hamiltonian = matrix element of the Hamiltonian H I = nuclear spin I = nuclear spin operator /r( ), /m( ) = energy distributions of Mossbauer y-rays = Boltzmann constant k = wave vector L(E) = Lorentzian line M = mass of nucleus Ml = magnetic dipole transition m = spin projection onto the quantization axes = 1 — a — i/3 = the complex index of refraction p = vector of electric dipole moment P = probability of a nuclear transition = tensor of the electric quadrupole q = eZ = nuclear charge R = reflectivity = radius-vector of the pth proton = mean-square radi-S = electronic spin T = temperature v =... 

The CN radical in its 21 ground state shows fine and hyperfine structure of the rotational levels which is more conventional than that of CO+, in that the largest interaction is the electron spin rotation coupling../ is once more a good quantum number, and the effective Hamiltonian is that given in equation (10.45), with the addition of the nuclear electric quadrupole term given in chapter 9. The matrix elements in the conventional hyperfine-coupled case (b) basis set were derived in detail in chapter 9,... 

The theory of the magnetic hyperfine interactions in NCI is essentially the same as that already described for the PF radical in the previous section, except that the nuclear spins / are 1 for 14N and 3/2 for 35C1. The form of the effective Hamiltonian for the quadrupole interaction and its matrix elements for two different quadrupolar nuclei was described in some detail in chapter 8 when we discussed the electric resonance spectra of CsF and LiBr. We now use the same case (b) hyperfine-coupled basis set as was used for PF. The quadrupole Hamiltonian for the two nuclei can be written as the sum of two independent terms as follows ... 

Let us apply the Redfield theory to a deuteron with its quadrupole moment experiencing a fluctuating electric field gradient arising from anisotropic molecular motions in liquids. When the static average of quadrupole interaction is nonzero, i.e. 0, it can be included in the static Hamiltonian Hq. The density operator matrix for a deuteron spin is of the dimension 3x3 and the corresponding Redfield relaxation supermatrix has the dimension V- x 3. When only nuclear spin-lattice relaxation is considered, the spin precession term in Equation [22] is set to zero and the diagonal elements 2, 3)... 

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