Commutation relations state-dependent operators

It is inevitable that one be selective in choosing topics for a book such as this. This book emphasizes ground state MO theory of molecules more than do most introductory texts, with rather less emphasis on spectroscopy than is usual. Angular momentum is treated at a fairly elementary level at various appropriate places in the text, but it is never given a ftiU-blown formal development using operator commutation relations. Time-dependent phenomena are not included. Thus, scattering theory is absent,... 

Linear terms are absent because of the Brillouin theorem. The coefficients Ap p. and Bap p, can be calculated by equating the nonzero matrix elements of the RPA Hamiltonian [Eq. (122)], in the basis of Eq. (121), to the corresponding matrix elements of the exact Hamiltonian [Eq. (23)] in the same basis. From the translational symmetry of the mean field states it follows that the A and B coefficients do not depend on the complete labels P = n, i, K and P = n, /, K1, but only on the sublattice labels /, AT and /, K. The second ingredient of the RPA formalism is that we assume boson commutation relations for the excitation and de-excitation operators (Raich and Etters, 1968 Dunmore, 1972). 

In classical mechanics, positions and momenta are treated on an equal footing in the Hamiltonian picture. In quantum mechanics, they become operators, but it is true that the position r and momentum p of a particle are appropriate conjugate variables that can entirely equivalently describe a state of a system under the commutation relation [r, p] = i (Dirac, 1958). This equivalence is usually demonstrated by the example of the onedimensional harmonic oscillator. The choice of the most appropriate representation depends on convenient description of the phenomenon considered. Generally, the position representation is useful for most bound-state problems such as atomic and molecular electronic structures as well as for many scattering problems. The momentum-space treatment... 

We now determine particular classes of commutation relations that are, indeed, conserved upon transformation to state-independent effective operators. The proof of (4.1) demonstrates that the preservation of [A, B] by definition A requires the existence of a relation between K, K, or both and one or both of the true operators A or B. Likewise, there must be a relation between the appropriate wave operator, the inverse mapping operator, or both, and A, B, or both for other state-independent effective operator definitions to conserve [A, B]. All mapping operators depend on the spaces and fl. Although the model space is often specified by selecting eigenfunctions of a zeroth order Hamiltonian, it may, in principle, be arbitrarily defined. On the other hand, the space fl necessarily depends on H. Therefore, the existence of a relation between mapping operators and A, B, or both, implies a relation between H and A, B, or both. 

The commutation relation between two arbitrary operators is not conserved upon transformation to effective operators by any of the definitions. Many state-independent effective operator definitions preserve the commutation relations involving // or a constant of the motion, as well as those involving operators which are related to P in a special way, for example, A with [P, 4] = 0. Many state-dependent definitions also conserve these special commutation relations. However, state-dependent definitions are not as convenient for formal and possibly computational reasons. The most important preserved commutation relations are those involving observables, since, as discussed in Section VII, they ensure that the basic symmetries of the system are conserved in effective Hamiltonian calculations. 

Semi-empirical Hamiltonians and operators are taken to be state independent [56] and have the same Hermiticity as their true counterparts. Consequently, the valence shell effective Hamiltonians and operators they mimic must also have these two properties. Table I shows that the effective Hani iltonian and operator definitions H and A, as well as H and either A or a fulfill these criteria. Thus, these definition pairs may be used to derive the valence shell effective Hamiltonians and operators mimicked by the semi-empirical methods. Table III indicates that the commutation relation (4.12) is preserved by all three definition pairs. Hence, the validity of the relations derived from the semi-empirical version of (4.12) depends on the extent to which the semi-empirical Hamiltonians and operators actually mimic, respectively, exact valence shell effective Hamiltonians and operators. In particular, the latter Hamiltonians and operators contain higher-body terms which are neglected, or ignored, in semi-empirical theories. These nonclassical higher body interactions have been shown to be nonnegligible for the valence shell Hamiltonians of many atoms and molecules [27, 145-149] and for the dipole moment operators of some small molecules [56-58]. There is no a... 

When many-body interactions are weak, l f,o(N — l,j) Fi(N — l,j) and the states i f s (N - l,j) have essentially no spectral weight for s > 0, that is, the (N — 1) electron state is close to the frozen orbital state. The many-body matrix element then reduces to the one-electron matrix element mj [ < f(cf,lr) A(t) Pj < j(cj)> with the vector potential A(f) = Aoexp(—2 rivt) from the harmonic long wavelength radiation field (dipole approximation). The time-dependent factors in the wave functions and vector potential produce, after integration, the factor 5(cf — ej — hv), which is the one-electron approximation to the 5-function already anticipated in Eq. (3.2.2.4) and which reflects the conservation of energy. We have then for the matrix element (p(( (,k) Ao Pj j(cj)) where all the time-dependent factors have been removed. Owing to commutation relations, the operator Ao pj can be replaced by the operator A0 rj [19]. The practical form ofthe dipole matrix element for the emission from localized core levels is then... 

---