Matrix elements of angular momentum

IV. MATRIX ELEMENTS OF ANGULAR-MOMENTUM-ADOPTED GAUSSIAN FUNCTIONS... 

IV. Matrix Elements of Angular-Momentum-Adopted Gaussian Functions... 

Since many of the operators that appear in the exact Hamiltonian or in the effective Hamiltonian involve products of angular momenta, some elementary angular momentum properties are summarized in the next section. Matrix elements of angular momentum products are frequently difficult to calculate. A tremendous simplification is obtained by working with spherical tensor operator components and, in this way, making use of the Wigner-Eckart Theorem (Section 3.4.5). A more elementary but cumbersome treatment, based on Cartesian operator components, is presented in Section 2.3. 

Chapters 2, 3, and 5 form the core of this book. Perturbations are defined and simple procedures for evaluating matrix elements of angular momentum operators are presented in Chapter 2. Chapter 3 deals with the troublesome terms in the molecular Hamiltonian that are responsible for perturbations. Particular attention is devoted to the reduction of matrix elements to separately evaluable rotational, vibrational, and electronic factors. Whenever possible the electronic factor is reduced to one- and two-electron orbital matrix elements. The magnitudes and physical interpretations of matrix elements are discussed in Chapter 5. In Chapter 4 the process of reducing spectra to molecular constants and the difficulty of relating empirical-parameters to terms in the exact molecular Hamiltonian are described. Transition intensities, especially quantum mechanical interference effects, are discussed in Chapter 6. Also included in Chapter 6 are examples of experiments that illustrate, sample, or utilize perturbation effects. The phenomena of predissociation and autoionization are forms of perturbation and are discussed in Chapters 7 and 8. 

Table 2 Useful relationships for the use of spherical tensors in the calculation of matrix elements of angular momentum operators (courtesy of Prof. JM Brown, PTCL, Oxford University)...

In the following, we pay special attention to the connections among the spherical, Stark and Zeeman basis. Since in momentum space the orbitals are simply related to hyperspherical harmonics, these connections are given by orthogonal matrix elements similar (when not identical) to the elements of angular momentum algebra. 

To form the only non-zero matrix elements of Hrot within the J, M, K> basis, one can use the following properties of the rotation-matrix functions (see, for example, Zare s book on Angular Momentum) ... 

The only difference is that a(0) is now an operator acting in jm) space of angular momentum eigenfunctions. This space consists of an infinite number of states, unlike those discussed above which had only four. This complication may be partly avoided if one takes into account that the scalar product in Eq. (4.55) does not depend on the projection index m. From spherical isotropy of space, Eq. (4.55) may be expressed via reduced matrix elements (/ a(0 /) as follows... 

Another important property of the angular momentum is the Wigner-Eckart theorem.2 This theorem states that the matrix elements of any tensor operator can be separated into two parts, one containing the m dependence and one independent of m,... 

On account of the hermiticity of the operators, only even values of L are allowed. Since the D operators are tensor operators of rank 1, the only allowed values are L = 0,2. The L = 0 contribution has been treated in type (1). Hence, only the L = 2 contribution must be considered here. The matrix elements of the operators (4.122) with L = 2 are difficult to evaluate. Nonetheless, by making use of the angular momentum algebra, they can be evaluated in explicit... 

Quantitative theories for the chemical shift and nuclear spin-spin interaction were developed by Ramsey (113) soon after the experimental discoveries of the effects. Unfortunately the complete treatments of these effects involve rather detailed knowledge of the electronic structures of molecules and require evaluation of matrix elements of the orbital angular momentum between ground and excited electronic states. These matrix elements depend sensitively on the behavior of the wave function near... 

The total angular momentum basis is thus computationally more efficient, even for collision problems in external fields. There is a price to pay for this. The expressions for the matrix elements of the collision Hamiltonian for open-shell molecules in external fields become quite cumbersome in the total angular momentum basis. Consider, for example, the operator giving the interaction of an open-shell molecule in a 51 electronic state with an external magnetic field. In the uncoupled basis (8.43), the matrix of this operator is diagonal with the matrix elements equal to Mg, where is the projection of S on the magnetic field axis. In order to evaluate the matrix elements of this operator in the coupled basis, we must represent the operator 5 by spherical tensor of rank 1 (Sj = fl theorem [5]... 

The introduction of modest rhombic terms (E < < D) mixes the doublets because of the off-diagonal matrix elements in E. This causes g and gy to separate second-order effects slightly reduce the average value of g, and gy and cause g to fall below 2. Unlike the S = f system discussed earlier, S = states are not orbital singlets, and there is the possibility of angular momentum contributions from admixture of d orbitals. This effect will be stronger if the separation between orbitals is small and if the unpaired electron density is localized on the metal... 

The exploitation of the community of the transformation properties of irreducible tensors and wave functions gives us the opportunity to deduce new relationships between the quantities considered, to further simplify the operators, already expressed in terms of irreducible tensors, or, in general, to offer a new method of calculating the matrix elements. Indeed, it is possible to show that the action of angular momentum operator Lf on the wave function, considered as irreducible tensor tp, may be represented in the form [86] ... 

The elements of the theory of angular momentum and irreducible tensors presented in this chapter make a minimal set of formulas necessary when calculating the matrix elements of the operators of physical quantities for many-electron atoms and ions. They are equally suitable for both non-relativistic and relativistic approximations. More details on this issue may be found in the monographs [3, 4, 9, 11, 12, 14, 17]. 

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